A polyol block copolymer, compositions and processes therefor

ABSTRACT

A process for producing a polyol block copolymer in a multiple reactor system including a first and second reactor in which a first reaction takes place in the first reactor and a second reaction takes place in the second reactor. The first reaction is the reaction of a carbonate catalyst with CO 2  and epoxide, in the presence of starter and/or solvent to produce polycarbonate polyol copolymer and the second reaction is the reaction of DMC catalyst with the polycarbonate polyol compound of the first reaction and epoxide to produce polyol block copolymer. The product of the first reaction is fed into the second as crude reaction mixture, the epoxide and the polycarbonate polyol compound of the first reaction are fed in a continuous or semi-batch manner, and/or the product of the first reaction has neutral or alkaline pH on addition to the second. The invention further relates to the copolymers and products incorporating such copolymers.

TECHNICAL FIELD

The present invention relates to the process of producing a polyol blockcopolymer from a two step process carried out in two separate reactors,and products and compositions incorporating such copolymers.

BACKGROUND

WO2015059068 and US 2015/0259475 (Equivalent of EP2888309) from Covestrodisclose the use of a DMC catalyst for the production of polyethercarbonate polyols from CO₂ and alkylene oxide in the presence of astarter compound. Many H-functional starter compounds are listedincluding polyether carbonate polyols, polycarbonate polyols andpolycarbonates. However, a DMC catalyst alone is limited in the amountof carbon dioxide it can incorporate into a polyethercarbonate polyol,requiring high pressures (generally more than 40 bar) to achieve amaximum of around 50% of the possible CO₂ incorporation. Furthermore, aDMC catalyst requires a pre-activation step, usually in the absence ofCO₂, which initially produces a polyether. CO₂ is then added andincorporated into the polymer structure. This means that a DMC catalystalone cannot produce low molecular weight polyols (e.g. <1000 Mn) withsubstantial CO₂ content and the CO₂ content of the polyol is evenrestricted at higher weights such as 2000 Mn. Polyethercarbonate polyolsproduced by a DMC alone generally have a structure which is rich inether linkages in the centre of the polymer chain and richer incarbonate groups towards the hydroxyl terminal groups. This is notadvantageous as the ether groups are substantially more stable to heatand basic conditions than the carbonate linkages.

WO2010062703 discloses production of block copolymers having apolycarbonate block and a hydrophilic block (e.g. a polyether). A twopot production is described, using a carbonate catalyst in the firstreaction to produce an alternating polycarbonate block, followed byquenching of the reaction, isolation of the polyol from solvents andunreacted monomers and then a second batch reaction with a DMC catalyst(in the absence of CO₂) to incorporate the hydrophilic oligomer, such aspoly(alkylene oxide). The process can be used to produce B-A-B polymerswhere A is a polycarbonate and B is a hydrophilic block such as apolyether. The polymers have use in enhanced oil recovery.

The invention allows production of polycarbonate block polyether polyolscontaining significantly increased CO₂ content under mild pressures byusing low molecular weight CO₂ containing polycarbonate polyols(produced by a carbonate catalyst in a first reaction) as starters for areaction between DMC catalyst and epoxide. Unlike the polyethercarbonate polyols produced by a DMC catalyst alone, the polycarbonateblock polyether polyols produced by the invention can produce lowmolecular weight polyols (e.g. <1000 Mn) with substantial CO₂ content(e.g. >7 wt %).

Advantageously, the low molecular weight polycarbonate polyols do nothave to be isolated but can be made in one reactor and transferreddirectly into the second without removing any catalyst, or solvents.

WO2017037441 describes a process where a carbonate catalyst and a DMCcatalyst are used in one reactor to produce a polyethercarbonate polyol.The conditions of the reaction must be balanced to meet the needs of twodifferent catalysts.

Advantageously, the invention allows optimisation of the conditions foruse of two different types of catalyst, a carbonate catalyst and a DMCcatalyst, enabling optimisation of conditions for each catalystindividually rather than compromising to suit the overall system. Thehigh carbonate content polyol can also be added directly to apre-activated DMC catalyst, which is more desirable as it reduces cycletimes and increases process safety by limiting unreacted epoxide contentin the reactor.

Furthermore, the invention can be used to produce polycarbonate blockpolyether polyol block copolymers which contain a core of high carbonatecontent chains with a terminal block of polyether chains. Polyurethanesmade from such polyols benefit from the advantages of high carbonatelinkages (e.g. increased strength, increased chemical resistance,resistance to both hydrolysis and oil etc) whilst still retaining thehigher thermal stability that ether end blocks provide. The polyols canadvantageously be made using the same or similar epoxide reactants inboth reactions.

SUMMARY OF THE INVENTION

According to the first aspect of the present invention, there is alsoprovided a process for producing a polyol block copolymer in a multiplereactor system; the system comprising a first and second reactor whereina first reaction takes place in the first reactor and a second reactiontakes place in the second reactor; wherein the first reaction is thereaction of a carbonate catalyst with CO₂ and epoxide, in the presenceof a starter and/or solvent to produce a polycarbonate polyol copolymerand the second reaction is the reaction of a DMC catalyst with thepolycarbonate polyol compound of the first reaction and epoxide toproduce a polyol block copolymer, wherein the product of the firstreaction is fed into the second reactor as a crude reaction mixture,(ii) the epoxide and the polycarbonate polyol compound of the firstreaction are fed into the second reactor in a continuous or semi-batchmanner, and/or (iii) the product of the first reaction has a neutral oralkaline pH on addition to the second reaction.

According to the second aspect of the present invention, there is alsoprovided a process process for producing a polyol block copolymer in amultiple reactor system; the system comprising a first and secondreactor wherein a first reaction takes place in the first reactor and asecond reaction takes place in the second reactor; wherein the firstreaction is the reaction of a carbonate catalyst with CO₂ and epoxide,in the presence of a polyfunctional starter, and optionally a solvent,to produce a polycarbonate polyol and the second reaction is thesemi-batch or continuous reaction of a DMC catalyst with thepolycarbonate polyol compound of the first reaction and epoxide toproduce a polyol block copolymer.

Adding the components in the separate reactions and reactors may beuseful to increase activity of the catalysts and may lead to a moreefficient process, compared with a process in which all of the materialsare provided at the start of one reaction. Large amounts of some of thecomponents present throughout the reaction may reduce efficiency of thecatalysts. Reacting this material in separate reactors may prevent thisreduced efficiency of the catalysts and/or may optimise catalystactivity. The reaction conditions of each reactor can be tailored tooptimise the reactions for each catalyst.

Additionally, not loading the total amount of each component at thestart of the reaction and having the catalyst for the first reaction ina separate reactor to the catalyst for the second reaction, may lead toeven catalysis, and more uniform polymer products. This in turn may leadto polymers having a narrower molecular weight distribution, desiredratio and distribution along the chain of ether to carbonate linkages,and/or improved polyol stability.

Having the reactions with the two different catalysts separate andmixing only certain components in the first reaction and adding theremainder in the second reaction may also be useful as the DMC catalystcan be pre-activated. Such pre-activation may be achieved by mixing oneor both catalysts with epoxide (and optionally other components).Pre-activation of the DMC catalyst is useful as it enables safe controlof the reaction (preventing uncontrolled increase of unreacted monomercontent) and removes unpredictable activation periods.

It will be appreciated that the present invention relates to a reactionin which carbonate and/or ether linkages are added to a growing polymerchain. Having separate reactions allows the first reaction to proceedbefore a second stage in the reaction. Mixing epoxide, carbonatecatalyst, starter compound and carbon dioxide, may permit growth of apolymer having a high number of carbonate linkages. Thereafter, addingthe products to the DMC catalyst in the absence of CO₂ permits thereaction to proceed by adding ether linkages to the growing polymerchain. Ether linkages are more thermally stable than carbonate linkagesand less prone to degradation by bases such as the amine catalysts usedin PU formation. Therefore, applications get the benefits of highcarbonate linkages (such as increased strength, chemical resistance,both oil and hydrolysis resistance etc) that are introduced from the Ablock whilst retaining the stability of the polyol through the etherlinkages from the B blocks at the ends of the polymer chains.

In general terms, an aim of the present invention is to control thepolymerisation reaction through a two-reactor system, to increase CO₂content of the polyols at low pressures (enabling more cost effectiveprocesses and plant design) and making a product that has high CO₂content but good stability and application performance. The processesherein may allow the product prepared by such processes to be tailoredto the necessary requirements.

The polyol block copolymers of the present invention may be preparedfrom a suitable epoxide and carbon dioxide in the presence of a startercompound and a carbonate catalyst for the first reaction; and then asuitable epoxide in the presence of a double metal cyanide (DMC)catalyst in the second reaction.

Although typically any residual CO₂ from the first reaction may beremoved from the crude reaction product of the first reaction prior tocommencement of the second reaction such that the second reaction iscarried out without CO₂, it will be appreciated that a small amount ofCO₂ may be present in the second reaction mixture as an unused reagentof the first reaction.

Typically the first reaction mixture contains less than 5% CO₂ by weightof the reaction mixture prior to addition to the second reaction,preferably less than 2.5%, such as less than 1.0%, less than 0.5% orless than 0.1%. Typically, the second reaction is carried out withoutthe independent addition of CO₂. The polyether block produced in thesecond reaction may have less than 1% carbonate linkages, preferablyless than 0.5% carbonate linkages, more preferably less than 0.1%carbonate linkages. Preferably the polyether block produced in thesecond reaction is substantially free from carbonate linkages.

Typically, therefore the second reaction is carried out substantially inthe absence of CO₂. Accordingly, by substantially in the absence of CO₂is meant that the second reaction is carried out in the presence of lessthan 4% CO₂ by weight, preferably less than 2%, such as less than 1.0%,less than 0.5% or less than 0.1% by weight of total reactants, catalystand products in the second reaction.

By a crude reaction mixture is meant that the product of the reaction istypically not isolated prior to addition of the reaction mixture of thesecond reaction. Preferably, the reaction mixture undergoes no furtherprocessing steps prior to its addition to the second reaction.

The carbonate catalyst of the present invention may be a catalyst thatproduces a polycarbonate polyol with greater than 76% carbonatelinkages, preferably greater than 80% carbonate linkages, morepreferably greater than 85% carbonate linkages, most preferably greaterthan 90% carbonate linkages may be present in block A.

If the epoxide used is asymmetric (e.g. propylene oxide), the catalystmay produce polycarbonate polyols with a high proportion of head to taillinkages, such as greater than 70%, greater than 80% or greater than 90%head to tail linkages. Alternatively, the catalyst may producepolycarbonate polyols with no stereoselectivity, producing polyols withapproximately 50% head to tail linkages.

The carbonate catalyst may be heterogeneous or homogeneous.

The carbonate catalyst may be a mono-metallic, bimetallic ormulti-metallic homogeneous complex.

The carbonate catalyst may comprise phenol or phenolate ligands.

Typically, the carbonate catalyst may be a bimetallic complex comprisingphenol or phenolate ligands. The two metals may be the same ordifferent.

The carbonate catalyst may be a catalyst of formula (IV):

(IV)

wherein:

M is a metal cation represented by M-(L)_(v);

x is an integer from 1 to 4, preferably x is 1 or 2;

is a multidentate ligand or plurality of multidentate ligands;

L is a coordinating ligand, for example, L may be a neutral ligand, oran anionic ligand that is capable of ring-opening an epoxide;

v is an integer that independently satisfies the valency of each M,and/or the preferred coordination geometry of each M or is such that thecomplex represented by formula (IV) above has an overall neutral charge.For example, each v may independently be 0, 1, 2 or 3, e.g. v may be 1or 2. When v>1, each L may be different.

The term multidentate ligand includes bidentate, tridentate,tetradentate and higher dentate ligands. Each multidentate ligand may bea macrocyclic ligand or an open ligand.

Such catalysts include those in WO2010022388 (metal salens andderivatives, metal porphyrins, corroles and derivatives, metal tetraazaannulenes and derivatives), WO2010028362 (metal salens and derivatives,metal porphyrins, corroles and derivatives, metal tetraaza annulenes andderivatives), WO2008136591 (metal salens), WO2011105846 (metal salens),WO2014148825 (metal salens), WO2013012895 (metal salens), EP2258745A1(metal porphyrins and derivatives), JP2008081518A (metal porphyrins andderivatives), CN101412809 (metal salens and derivatives), WO2019126221(metal aminotriphenol complexes), U.S. Pat. No. 9,018,318 (metalbeta-diiminate complexes), U.S. Pat. No. 6,133,402A (metalbeta-diiminate complexes) and U.S. Pat. No. 8,278,239 (metal salens andderivatives), the entire contents of which, especially, insofar as theyrelate to suitable carbonate catalysts for the reaction of CO₂ andepoxide, in the presence of a starter and optionally a solvent toproduce a polycarbonate polyol copolymer as defined herein areincorporated herein by reference. Such catalysts also include those inWO2009/130470, WO2013/034750, WO2016/012786, WO2016/012785, WO2012037282and WO2019048878A1 (all bimetallic phenolate complexes), the entirecontents of which, especially, insofar as they relate to suitablecarbonate catalysts for the reaction of CO₂ and epoxide, in the presenceof a starter and optionally a solvent to produce a polycarbonate polyolcopolymer as defined herein are incorporated herein by reference.

The carbonate catalyst may have the following structure:

wherein:

M₁ and M₂ are independently selected from Zn(II), Cr(II), Co(II),Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X,Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X,Ti(III)-X, V(III)-X, Ge(IV)-(X)₂, Y(III)-X, Sc(III)-X or Ti(IV)-(X)₂;

R₁ and R₂ are independently selected from hydrogen, halide, a nitrogroup, a nitrile group, an imine, an amine, an ether, a silyl group, asilyl ether group, a sulfoxide group, a sulfonyl group, a sulfinategroup or an acetylide group or an optionally substituted alkyl, alkenyl,alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio,arylthio, alicyclic or heteroalicyclic group;

R₃ is independently selected from optionally substituted alkylene,alkenylene, alkynylene, heteroalkylene, heteroalkenylene,heteroalkynylene, arylene, heteroarylene or cycloalkylene, whereinalkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene andheteroalkynylene, may optionally be interrupted by aryl, heteroaryl,alicyclic or heteroalicyclic;

R₅ is independently selected from H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylheteroaryl or alkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

E₃, E₄, E₅ and E₆ are selected from N, NR₄, O and S, wherein when E₃,E₄, E₅ or E₆ are N,

and wherein when E₃, E₄, E₅ or E₆ are NR₄, O or S,

is

R₄ is independently selected from H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylheteroaryl, -alkylC(O)OR₁₉ or -alkylC≡N or alkylaryl;

X is independently selected from OC(O)R_(x), OSO₂R_(x), OSOR_(x),OSO(R_(x))₂, S(O)R_(x), OR_(x), phosphinate, phosphonate, halide,nitrate, hydroxyl, carbonate, amino, nitro, amido or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, arylor heteroaryl, wherein each X may be the same or different and wherein Xmay form a bridge between M₁ and M₂;

R_(x) is independently hydrogen, or optionally substituted aliphatic,haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,alkylaryl or heteroaryl; and G is absent or independently selected froma neutral or anionic donor ligand which is a Lewis base.

Each of the occurrences of the groups R₁ and R₂ may be the same ordifferent, and R₁ and R₂ can be the same or different.

DMC catalysts are complicated compounds which comprise at least twometal centres and cyanide ligands. The DMC catalyst may additionallycomprise at least one of: one or more complexing agents, water, a metalsalt and/or an acid (e.g. in non-stoichiometric amounts). The first twoof the at least two metal centres may be represented by M′ and M″.

M′ may be selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II),Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI),Sr(II), W(IV), W(VI), Cu(II), and Cr(III), M′ is optionally selectedfrom Zn(II), Fe(II), Co(II) and Ni(II), optionally M′ is Zn(II).

M″ is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III),Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V),optionally M″ is selected from Co(II), Co(III), Fe(II), Fe(III),Cr(III), Ir(III) and Ni(II), optionally M″ is selected from Co(II) andCo(III).

It will be appreciated that the above optional definitions for M′ and M″may be combined. For example, optionally M′ may be selected from Zn(II),Fe(II), Co(II) and Ni(II), and M″ may optionally be selected fromCo(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). Forexample, M′ may optionally be Zn(II) and M″ may optionally be selectedfrom Co(II) and Co(III).

If a further metal centre(s) is present, the further metal centre may befurther selected from the definition of M′ or M″.

Examples of DMC catalysts which can be used in the process of theinvention include those described in U.S. Pat. Nos. 3,427,256,5,536,883, 6,291,388, 6,486,361, 6,608,231, 7,008,900, 5,482,908,5,780,584, 5,783,513, 5,158,922, 5,693,584, 7,811,958, 6,835,687,6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953,4,500,704, 7,977,501, 9,315,622, EP-A-1568414, EP-A-1529566, and WO2015/022290, the entire contents of which, especially, insofar as theyrelate to DMC catalysts for the production of the block copolymer asdefined herein or reactions as defined herein, are incorporated hereinby reference.

It will be appreciated that the DMC catalyst may comprise:

M′_(d)[M″_(e)(CN)_(f)]_(g)

wherein M′ and M″ are as defined above, d, e, f and g are integers, andare chosen such that the DMC catalyst has electroneutrality. Optionally,d is 3. Optionally, e is 1. Optionally f is 6. Optionally g is 2.Optionally, M′ is selected from Zn(II), Fe(II), Co(II) and Ni(II),optionally M′ is Zn(II). Optionally M″ is selected from Co(II), Co(III),Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), optionally M″ is Co(II) orCo(III).

It will be appreciated that any of these optional features may becombined, for example, d is 3, e is 1, f is 6 and g is 2, M′ is Zn(II)and M″ is Co(III).

Suitable DMC catalysts of the above formula may include zinchexacyanocobaltate(III), zinc hexacyanoferrate(III), nickelhexacyanoferrate(II), and cobalt hexacyanocobaltate(III).

There has been a lot of development in the field of DMC catalysts, andthe skilled person will appreciate that the DMC catalyst may comprise,in addition to the formula above, further additives to enhance theactivity of the catalyst. Thus, while the above formula may form the“core” of the DMC catalyst, the DMC catalyst may additionally comprisestoichiometric or non-stoichiometric amounts of one or more additionalcomponents, such as at least one complexing agent, an acid, a metalsalt, and/or water.

For example, the DMC catalyst may have the following formula:

M′_(d)[M″_(e)(CN)_(f)]_(g) .hM″′X″_(i) .jR^(c) .kH₂O.lH_(r)X″′

wherein M′, M″, X″′, d, e, f and g are as defined above. M″ can be M′and/or M″. X″ is an anion selected from halide, oxide, hydroxide,sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate,isothiocyanate, carboxylate and nitrate, optionally X″ is halide. i isan integer of 1 or more, and the charge on the anion X″ multiplied by isatisfies the valency of M″. r is an integer that corresponds to thecharge on the counterion X″′. For example, when X′″ is Cl⁻, r will be 1.l is 0, or a number between 0.1 and 5. Optionally, l is between 0.15 and1.5.

R^(c) is a complexing agent or a combination of one or more complexingagents. For example, R^(c) may be a (poly)ether, a polyether carbonate,a polycarbonate, a poly(tetramethylene ether diol), a ketone, an ester,an amide, an alcohol (e.g. a C₁₋₈ alcohol), a urea and the like, such aspropylene glycol, polypropylene glycol, (m)ethoxy ethylene glycol,dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether,diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butylalcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol,2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol ora combination thereof, for example, R^(c) may be tert-butyl alcohol,dimethoxyethane, or polypropylene glycol.

As indicated above, more than one complexing agent may be present in theDMC catalysts used in the present invention. Optionally one of thecomplexing agents of R_(c) may be a polymeric complexing agent.Optionally, R_(c) may be a combination of a polymeric complexing agentand a non-polymeric complexing agent. Optionally, a combination of thecomplexing agents tert-butyl alcohol and polypropylene glycol may bepresent.

It will be appreciated that if the water, complexing agent, acid and/ormetal salt are not present in the DMC catalyst, h, j, k and/or l will bezero respectively. If the water, complexing agent, acid and/or metalsalt are present, then h, j, k and/or l are a positive number and may,for example, be between 0 and 20. For example, h may be between 0.1 and4. j may be between 0.1 and 6. k may be between 0 and 20, e.g. between0.1 and 10, such as between 0.1 and 5. l may be between 0.1 and 5, suchas between 0.15 and 1.5.

The polymeric complexing agent is optionally selected from a polyether,a polycarbonate ether, and a polycarbonate. The polymeric complexingagent may be present in an amount of from about 5% to about 80% byweight of the DMC catalyst, optionally in an amount of from about 10% toabout 70% by weight of the DMC catalyst, optionally in an amount of fromabout 20% to about 50% by weight of the DMC catalyst.

The DMC catalyst, in addition to at least two metal centres and cyanideligands, may also comprise at least one of: one or more complexingagents, water, a metal salt and/or an acid, optionally innon-stoichiometric amounts.

An exemplary DMC catalyst is of the formulaZn₃[Co(CN)₆]₂.hZnCl₂.kH₂O.j[(CH₃)₃COH], wherein h, k and j are asdefined above. For example, h may be from 0 to 4 (e.g. from 0.1 to 4), kmay be from 0 to 20 (e.g. from 0.1 to 10), and j may be from 0 to 6(e.g. from 0.1 to 6). As set out above, DMC catalysts are complicatedstructures, and thus, the above formulae including the additionalcomponents is not intended to be limiting. Instead, the skilled personwill appreciate that this definition is not exhaustive of the DMCcatalysts which are capable of being used in the invention.

The DMC catalyst may be pre-activated. Such pre-activation may beachieved by mixing one or both catalysts with alkylene oxide (andoptionally other components). Pre-activation of the DMC catalyst isuseful as it enables safe control of the reaction (preventinguncontrolled increase of unreacted monomer content) and removesunpredictable activation periods. Optionally, the DMC catalyst may bepre-activated in reactor 2 or separately. Optionally, the DMC catalystmay be pre-activated with a starter compound or with the reactionproduct of the first or second reaction. When the DMC catalyst ispre-activated with the reaction product of the first reaction, it may bepre-activated with some or all of the reaction product of the firstreaction. The DMC catalyst may be pre-activated with the polyol blockcopolymer product which may be added into the reactor, or may be theremaining product from a previous reaction, the so-called ‘reactionheel’.

The starter compound which may be used in the processes for formingpolycarbonate polyols of the present invention comprises at least onegroup, preferably at least two groups, selected from a hydroxyl group(—OH), a thiol (—SH), an amine having at least one N—H bond (—NHR′), agroup having at least one P—OH bond (e.g. —PR′(O)OH, PR′(O)(OH)₂ or—P(O)(OR′)(OH)), or a carboxylic acid group (—C(O)OH). Where the starteris a polyfunctional starter compound, the starter compound comprises atleast two groups selected from a hydroxyl group (—OH), a thiol (—SH), anamine having at least one N—H bond (—NHR′), a group having at least oneP—OH bond (e.g. PR′(O)OH, PR′(O)(OH)₂ or —P(O)(OR′)(OH)), or acarboxylic acid group (—C(O)OH).

Thus, the starter compound which may be used in the processes forforming polycarbonate ether polyols may be of the formula (III):

Z—(R^(Z))_(a)  (III)

Z can be any group which can have 1 or more —R^(Z) groups attached toit, preferably 2 or more —R^(z) groups attached to it. Thus, Z may beselected from optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene,cycloalkenylene, hererocycloalkylene, heterocycloalkenylene, arylene,heteroarylene, or Z may be a combination of any of these groups, forexample Z may be an alkylarylene, heteroalkylarylene,heteroalkylheteroarylene or alkylheteroarylene group. Optionally Z isalkylene, heteroalkylene, arylene, or heteroarylene.

a is an integer which is at least 1, preferably at least 2, optionally ais in the range of between 1 and 8, optionally a is in the range ofbetween 2 and 6.

Each R^(Z) may be OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), PR′(O)(OH)₂or PR′(O)OH, optionally R^(Z) is selected from —OH, —NHR′ or —C(O)OH,optionally each R^(z) is —OH, —C(O)OH or a combination thereof (e.g.each R^(z) is —OH).

R′ may be H, or optionally substituted alkyl, heteroalkyl, aryl,heteroaryl, cycloalkyl or heterocycloalkyl, optionally R′ is H oroptionally substituted alkyl.

Z′ corresponds to R^(z), except that a bond replaces the labile hydrogenatom. Therefore, the identity of each Z′ depends on the definition ofR^(Z) in the starter compound. Thus, it will be appreciated that each Z′may be —O—, —NR′—, —S—, —C(O)O—, —P(O)(OR′)O—, —PR′(O)(O—)₂ or PR′(O)O—(wherein R′ may be H, or optionally substituted alkyl, heteroalkyl,aryl, heteroaryl, cycloalkyl or heterocycloalkyl, preferably R′ is H oroptionally substituted alkyl), preferably Z′ may be —C(O)O—, —NR′— or—O—, more preferably each Z′ may be —O—, —C(O)O— or a combinationthereof, more preferably each Z′ may be —O—.

More than one starter compound may be present in each reaction. Thestarter compounds for the first and second reaction may be the same ordifferent. Where there are two different starter compounds, there may betwo starter compounds in the second reaction, wherein the startercompound in the first reaction is a first starter compound, and whereinthe second reaction comprises adding the first crude reaction mixture tothe second reactor comprising a second starter compound and double metalcyanide (DMC) catalyst and, optionally, solvent and/or epoxide. Thesecond reaction of the present invention may be conducted at least about1 minutes after the first reaction, optionally at least about 5 minutes,optionally at least about 15 minutes, optionally at least about 30minutes, optionally at least about 1 hour, optionally at least about 2hours, optionally at least about 5 hours. It will be appreciated that ina continuous reaction these periods are the average period from additionof monomer in the first reactor to transfer of monomer residue into thesecond reactor.

If polymeric, the starter compound may have a molecular weight of atleast about 200 Da or of at most about 1000 Da.

For example, having a molecular weight of about 200 to 1000 Da,optionally about 300 to 700 Da, optionally about 400 Da.

The or each starter compound typically has one or more R^(z) groups,optionally two or more, optionally three or more, optionally four ormore, optionally five or more, optionally six or more, optionally sevenor more, optionally eight or more R^(z) groups, particularly whereinR^(z) is hydroxyl.

It will be appreciated that any of the above features may be combined.For example, a may be between 1 and 8, each R^(Z) may be —OH, —C(O)OH ora combination thereof, and Z may be selected from alkylene,heteroalkylene, arylene, or heteroarylene.

Exemplary starter compounds for either reaction include monofunctionalstarter substances such as alcohols, phenols, amines, thiols andcarboxylic acids; for example, alcohols such as methanol, ethanol, 1-and 2-propanol, 1- and 2-butanol, linear or branched C₃-C₂₀-monoalcoholsuch as tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol,2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol,1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol,2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol,2-octanol, 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol,2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl,2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, mono-ethersor esters of ethylene, propylene, polyethylene; polypropylene glycolssuch as ethylene glycol mono-methyl ether and propylene glycolmono-methyl ether, phenols such as linear or branched C₃-C₂₀ alkylsubstituted phenols, for example nonyl-phenols or octyl phenolsmonofunctional carboxylic acids such as formic acid, acetic acid,propionic acid and butyric acid, fatty acids, such as stearic acid,palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acidand acrylic acid, and monofunctional thiols such as ethanethiol,propane-1-thiol, propane-2-thiol, butane-1-thiol,3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol, or amines suchas butylamine, tert-butylamine, pentylamine, hexylamine, aniline,aziridine, pyrrolidine, piperidine, and morpholine; and/or selected fromdiols such as 1,2-ethanediol (ethylene glycol), 1-2-propanediol,1,3-propanediol (propylene glycol), 1,2-butanediol, 1-3-butanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol,1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexenediol,1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol,tripropylene glycol, triethylene glycol, tetraethylene glycol,polypropylene glycols (PPGs) or polyethylene glycols (PEGs) having an Mnof up to about 1500 g/mol, such as PPG 425, PPG 725, PPG 1000 and thelike, triols such as glycerol, benzenetriol, 1,2,4-butanetriol,1,2,6-hexanetriol, tris(methylalcohol)propane,tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylolpropane, polyethylene oxide triols, polypropylene oxide triols andpolyester triols, tetraols such as calix[4]arene,2,2-bis(methylalcohol)-1,3-propanediol, erythritol, pentaerythritol orpolyalkylene glycols (PEGs or PPGs) having 4-OH groups, polyols, such assorbitol or polyalkylene glycols (PEGs or PPGs) having 5 or more —OHgroups, or compounds having mixed functional groups includingethanolamine, diethanolamine, methyldiethanolamine, andphenyldiethanolamine.

For example, the starter compound may be a monofunctional alcohol suchas ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol,1-octanol, 1-decanol, 1-dodecanol, a phenol such as nonyl-phenol oroctyl phenol or a mono-functional carboxylic acid such as formic acid,acetic acid, propionic acid, butyric acid, fatty acids, such as stearicacid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoicacid, acrylic acid.

For example, the starter compound may be a diol such as 1,2-ethanediol(ethylene glycol), 1-2-propanediol, 1,3-propanediol (propylene glycol),1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentylglycol, catechol, cyclohexenediol, 1,4-cyclohexanedimethanol,poly(caprolactone) diol, dipropylene glycol, diethylene glycol,tripropylene glycol, triethylene glycol, tetraethylene glycol,polypropylene glycols (PPGs) or polyethylene glycols (PEGs) having an Mnof up to about 1500 g/mol, such as PPG 425, PPG 725, PPG 1000 and thelike. It will be appreciated that the starter compound may be1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol,poly(caprolactone) diol, PPG 425, PPG 725, or PPG 1000. Preferably thestarter compound may be a diol such as 1,2-ethanediol (ethylene glycol),1,3-propanediol (propylene glycol), 1,2-butanediol, 1-3-butanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol,1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexenediol,1,4-cyclohexanedimethanol, poly(caprolactone) diol, dipropylene glycol,diethylene glycol, tripropylene glycol, triethylene glycol,tetraethylene glycol, polypropylene glycols (PPGs) or polyethyleneglycols (PEGs) having an Mn of up to about 1500 g/mol, such as PPG 425,PPG 725, PPG 1000 and the like. It will be appreciated that the startercompound may be 1,6-hexanediol, 1,4-cyclohexanedimethanol,1,12-dodecanediol, poly(caprolactone) diol, PPG 425, PPG 725, or PPG1000.

Further exemplary starter compounds may include diacids such as oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid,dodecanedioic acid or other compounds having mixed functional groupssuch as lactic acid, glycolic acid, 3-hydroxypropanoic acid,4-hydroxybutanoic acid, 5-hydroxypentanoic acid.

The ratio of the starter compound, if present, to the carbonate catalystmay be in amounts of from about 1000:1 to about 1:1, for example, fromabout 750:1 to about 5:1, such as from about 500:1 to about 10:1, e.g.from about 250:1 to about 20:1, or from about 125:1 to about 30:1, orfrom about 50:1 to about 20:1. These ratios are molar ratios. Theseratios are the ratios of the total amount of starter to the total amountof the carbonate catalyst used in the processes. These ratios may bemaintained during the course of addition of materials.

The DMC catalyst may be pre-activated. Optionally, the DMC catalyst maybe pre-activated in reactor 2 or separately. Optionally, the DMCcatalyst may be pre-activated with a starter compound or with thereaction product of the first or second reaction. When the DMC catalystis pre-activated with the reaction product of the first reaction, it maybe pre-activated with some or all of the reaction product of the firstreaction. The DMC catalyst may be pre-activated with the polyol blockcopolymer product which may be added into the reactor, or may be theremaining product from a previous reaction, the so-called ‘reactionheel’.

The product of the first reaction may be a low molecular weightpolycarbonate polyol. The preferred molecular weight (Mn) of thepolycarbonate polyol depends on the preferred overall molecular weightof the polyol block copolymer. The molecular weight (Mn) of thepolycarbonate polyol may be in the range from about 200 to about 4000Da, from about 200 to about 2000 Da, from about 200 to about 1000 Da, orfrom about 400 to about 800 Da, as measured by Gel PermeationChromatography.

The first reaction may produce a generally alternating polycarbonatepolyol product.

The product of the first reaction may be fed into the separate reactorcontaining a pre-activated DMC catalyst. The first product may be fedinto the separate reactor as a crude reaction mixture.

The first reaction of the present invention may be carried out under CO₂pressure of less than 20 bar, preferably less than 10 bar, morepreferably less than 8 bar of CO₂ pressure.

The second reaction of the present invention may be carried out underCO₂ pressure of less than 60 bar, preferably less than 20 bar, morepreferably less than 10 bar, most preferably less than 5 bar of CO₂pressure.

The CO₂ may be added continuously in the first reaction, preferably inthe presence of a starter.

The first reaction may be carried out at a pressure of between about 1bar and about 60 bar carbon dioxide, optionally about 1 bar and about 40bar, optionally about 1 bar and about 20 bar, optionally between about 1bar and about 15 bar, optionally about 1 bar and about 10 bar,optionally about 1 bar and about 5 bar.

The second reaction may be carried out under reduced pressure or aninert gas such as N₂ or Ar. Any residual CO₂ remaining from the firstreaction may be stripped by gas stripping the reaction mixture or byapplying a vacuum to the reaction mixture. As discussed above, residualamounts of CO₂ may be present in the reaction mixture from the firstreaction but will be less than less than 5% CO₂ by weight of thereaction mixture prior to addition to the second reaction, preferablyless than 2.5%, less than 1.0%, less than 0.5% or less than 0.1%. Noadditional CO₂ is added during the second reaction. The product of thefirst reaction may be transferred to the second reaction under thepressure of unused CO₂ from the first reaction, but no further CO₂ isadded in the second reactor.

The first reaction process being carried out under these relatively lowCO₂ pressures and the CO₂ added continuously can produce a polyol withhigh CO₂ content, under low pressure. The CO₂ may be introduced into thefirst reactor via standard methods, such as directly into the headspaceor directly into the reaction liquid via standard methods such as ainlet tube, gassing ring or a hollow shaft stirrer. The mixing may beoptimised by using different configurations of stirrer, such as singleagitators or agitators configured in multiple stages.

The first reaction may be carried out in a batch, semi-batch orcontinuous process. In a batch process, all the carbonate catalyst,epoxide, CO₂, starter and optionally solvent are present at thebeginning of the reaction. In a semi-batch or continuous reaction, oneor more of the carbonate catalyst, epoxide, CO₂, starter and/or solventare added into the reactor in a continuous, semi-continuous ordiscontinuous manner.

The second reaction comprising DMC may be carried out as a continuousprocess or a semi-batch process. In a semi-batch or continuous processone or more of the DMC catalyst, epoxide starter and/or solvent is addedinto the reaction in a continuous or discontinuous manner.

Optionally, the crude reaction mixture fed into the second reactor mayinclude an amount of unreacted epoxide and/or starter.

Optionally, the crude reaction mixture feed may include an amount ofcarbonate catalyst.

Optionally, the carbonate catalyst may have been removed prior to theaddition to the second reactor.

The polycarbonate product of the first reaction may be referred to asthe crude product.

The polycarbonate product of the first reaction may be fed into thesecond reaction in a single slug or in a continuous, semi-continuous ordiscontinuous manner. Preferably, the product of the first reaction isfed into the second reactor in a continuous manner, optionallycontaining unreacted epoxide and/or carbonate catalyst. This isadvantageous as the continuous addition of the product of reaction 1 asa starter for the DMC catalyst allows the DMC catalyst in reactor 2 tooperate in a more controlled manner as the ratio of starter to DMCcatalyst is always reduced in the reactor. This may prevent deactivationof the DMC catalyst in reactor 2. The polycarbonate of reaction 1 may befed into the second reactor prior to DMC activation and may be usedduring the DMC activation. The DMC catalyst may also be pre-activatedwith the polyol block copolymer which may be added into the reactor, ormay be the remaining product from a previous reaction, the so-called‘reaction heel’.

The temperature of the reaction in the first reactor may be in the rangeof from about 0° C. to 250° C., preferably from about 40° C. to about160° C., more preferably from about 50° C. to 120° C.

The temperature of the reaction in the second reactor may be in therange from about 50 to about 160° C., preferably in the range from about70 to about 140° C., more preferably from about 80 to about 130° C.

The two reactors may be located in a series, or the reactors may benested. Each reactor may individually be a stirred tank reactor, a loopreactor, a tube reactor or other standard reactor design.

The first reaction may be carried in more than one reactor that feedsthe crude reaction mixture into the second reaction, and reactor,continuously. Preferably, reaction 2 is run in a continuous mode.

The product of the first reaction may be stored for subsequent later usein the second reactor.

Advantageously, the two reactions can be run independently to getoptimum conditions for each. If the two reactors are nested they may beeffective to provide different reaction conditions to each othersimultaneously.

Optionally, the polycarbonate polyol may not have been stabilised by anacid prior to addition to the second reactor.

If the polycarbonate polyol is stabilised by an acid prior to additionto the second reactor, the acid may be an inorganic or an organic acid.Such acids include, but are not limited to, phosphoric acid derivatives,sulfonic acid derivatives (e.g. methanesulfonic acid, p-toluenesulfonicacid), carboxylic acids (e.g. acetic acid, formic acid, oxalic acid,salicylic acid), mineral acids (e.g. hydrochloric acid, hydrobromicacid, hydroiodic acid), nitric acid or carbonic acid. The acid may bepart of an acidic resin, such as an ion exchange resin. Acidic ionexchange resins may be in the form of a polymeric matrix (such aspolystyrene or polymethacrylic acid) featuring acidic sites such asstrong acidic sites (e.g. sulfonic acid sites) or weak acid sites (e.g.carboxylic acid sites). Example ionic exchange resins include Amberlyst15, Dowex Marathon MSC and Amberlite IRC 748.

The first and second reactions of the present invention may be carriedout in the presence of a solvent, however it will also be appreciatedthat the processes may also be carried out in the absence of a solvent.When a solvent is present, it may be toluene, hexane, t-butyl acetate,diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene,methylene chloride, propylene carbonate, ethylene carbonate, acetone,ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF),etc. The solvent may be toluene, hexane, acetone, ethyl acetate andn-butyl acetate.

The solvent may act to dissolve one or more of the materials. However,the solvent may also act as a carrier, and be used to suspend one ormore of the materials in a suspension. Solvent may be required to aidaddition of one or more of the materials during the steps of theprocesses of the present invention.

The process may employ a total amount of solvent, and wherein about 1 to100% of the total amount of solvent may be mixed in the first reaction,with the remainder added in the second reaction; optionally with about 1to 75% being mixed in the first reaction, optionally with about 1 to50%, optionally with about 1 to 40%, optionally with about 1 to 30%,optionally with about 1 to 20%, optionally with about 5 to 20%.

The total amount of the carbonate catalyst may be low, such that thefirst reaction of the invention may be carried out at low catalyticloading. For example, the catalytic loading of the carbonate catalystmay be in the range of about 1:500-100,000 [total carbonatecatalyst]:[total epoxide], such as about 1:750-50,000 [total carbonatecatalyst]:[total epoxide], e.g. in the region of about 1:1,000-20,000[total carbonate catalyst]:[total epoxide], for example in the region ofabout 1:10,000 [total carbonate catalyst]:[total epoxide]. The ratiosabove are molar ratios. These ratios are the ratios of the total amountof carbonate catalyst to the total amount of epoxide used in the firstreaction.

The process may employ a total amount of epoxide, and about 1 to 100% ofthe total amount of epoxide may be mixed in the first reaction. Theremainder of epoxide may be added in the second reaction; withoptionally about 5 to 90% being mixed in the first reaction, optionallywith about 10 to 90%, optionally with about 20 to 90%, optionally withabout 40 to 90%, optionally with about 40 to 80%, optionally with about5 to 50%.

The epoxide which is used in the first and second reactions may be anysuitable compound containing an epoxide moiety. Exemplary epoxidesinclude ethylene oxide, propylene oxide, butylene oxide and cyclohexeneoxide. The epoxide(s) used for the second reaction may be the same ordifferent from the epoxide(s) used for the first reaction. Accordingly,a mixture of one or more epoxides may be present in one or both of thereactions. For example, the first reaction may comprise propylene oxideand the second reaction may comprise ethylene oxide, or both reactionsmay comprise ethylene oxide, or one or both reactions may use a mixtureof epoxides such as a mixture of ethylene oxide with propylene oxide.

The epoxide may be purified (for example by distillation, such as overcalcium hydride) prior to reaction with carbon dioxide. For example, theepoxide may be distilled prior to being added.

Examples of epoxides which may be used in the present invention include,but are not limited to, cyclohexene oxide, styrene oxide, ethyleneoxide, propylene oxide, butylene oxide, substituted cyclohexene oxides(such as limonene oxide, C₁₀H₁₆O or2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C₁₁H₂₂O), alkylene oxides(such as ethylene oxide and substituted ethylene oxides), unsubstitutedor substituted oxiranes (such as oxirane, epichlorohydrin,2-(2-methoxyethoxy)methyl oxirane (MEMO),2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO),2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO),1,2-epoxybutane, glycidyl ethers, glycidyl ester, glycidyl carbonates,vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 2,3-epoxybutane,isobutylene oxide, cyclopentene oxide,2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, andfunctionalized 3,5-dioxaepoxides. Examples of functionalized3,5-dioxaepoxides include:

The epoxide moiety may be a glycidyl ether, glycidyl ester or glycidylcarbonate. Examples of glycidyl ethers, glycidyl esters glycidylcarbonates include:

As noted above, the epoxide substrate may contain more than one epoxidemoiety, i.e. it may be a bis-epoxide, a tris-epoxide, or a multi-epoxidecontaining moiety. Examples of compounds including more than one epoxidemoiety include, bis-epoxybutane, bis-epoxyoctane, bis-epoxydecane,bisphenol A diglycidyl ether and3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate. It will beunderstood that reactions carried out in the presence of one or morecompounds having more than one epoxide moiety may lead to cross-linkingin the resulting polymer.

Optionally, between 0.1 and 20% of the total epoxide in the firstreaction may be an epoxide substrate containing more than one epoxidemoiety. Preferably, the multi-epoxide substrate is a bis-epoxide.

The skilled person will appreciate that the epoxide can be obtained from“green” or renewable resources. The epoxide may be obtained from a(poly)unsaturated compound, such as those deriving from a fatty acidand/or terpene, obtained using standard oxidation chemistries.

The epoxide moiety may contain —OH moieties, or protected OH moieties.The —OH moieties may be protected by any suitable protecting group.Suitable protecting groups include methyl or other alkyl groups, benzyl,allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl(C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT),methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such astrimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl(TBDPS), tri-iso-propylsilyloxymethyl (TOM), and triisepropylsilyI(TIPS)), (4-rnethoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl(THF), and tetrahydropyranyl (THP).

The epoxide optionally has a purity of at least 98%, optionally >99%.

The rate at which the materials are added may be selected such that thetemperature of the (exothermic) reactions does not exceed a selectedtemperature (i.e. that the materials are added slowly enough to allowany excess heat to dissipate such that the temperature of the remainsapproximately constant). The rate at which the materials are added maybe selected such that the epoxide concentration does not exceed aselected epoxide concentration.

The process may produce a polyol with a polydispersity between 1.0 and2.0, preferably between 1.0 and 1.8, more preferably between 1.0 and1.5, most preferably between 1.0 and 1.3.

The process may comprise mixing double metal cyanide (DMC) catalyst,epoxide, starter and optionally solvent to form a pre-activated mixtureand adding the pre-activated mixture to the second reactor either beforeor after the crude reaction mixture of the first reaction, to form thesecond reaction mixture. However, this may take place continuously sothat the pre-activated mixture is added at the same time as the crudereaction mixture. The pre-activated mixture may also be formed in thesecond reactor by mixing the DMC catalyst, epoxide, starter andoptionally solvent. The pre-activation may occur at a temperature ofabout 50° C. to 160° C., preferably between about 70° C. to 140° C.,more preferably about 90° C. to 140° C. The pre-activated mixture may bemixed at a temperature of between about 50 to 160° C. prior to contactwith the crude reaction mixture, optionally between about 70 to 140° C.

In the overall reaction process, the amount of said carbonate catalystand the amount of said double metal cyanide (DMC) catalyst may be at apredetermined weight ratio of from about 300:1 to about 1:100 to oneanother, for example, from about 120:1 to about 1:75, such as from about40:1 to about 1:50, e.g. from about 30:1 to about 1:30 such as fromabout 20:1 to about 1:1, for example from about 10:1 to about 2:1, e.g.from about 5:1 to about 1:5. The processes of the present invention canbe carried out on any scale. The process may be carried out on anindustrial scale. As will be understood by the skilled person, catalyticreactions are generally exothermic. The generation of heat during asmall-scale reaction is unlikely to be problematic, as any increase intemperature can be controlled relatively easily by, for example, the useof an ice bath. With larger scale reactions, and particularly industrialscale reactions, the generation of heat during a reaction can beproblematic and potentially dangerous. Thus, the gradual addition ofmaterials may allow the rate of the catalytic reaction to be controlledand can minimise the build-up of excess heat. The rate of the reactionmay be controlled, for example, by adjusting the flow rate of thematerials during addition. Thus, the processes of the present inventionhave particular advantages if applied to large, industrial scalecatalytic reactions.

The temperature may increase or decrease during the course of theprocesses of the invention.

The amount of said carbonate catalyst and the amount of said doublemetal cyanide (DMC) catalyst will vary depending on which carbonatecatalyst and DMC catalyst is used.

The product of the process of the first aspect of the invention is apolyol block copolymer. According to the third aspect of the invention,there is provided a polyol block copolymer comprising a polycarbonateblock, A (-A′-Z′—Z—(Z′-A′)_(n)-), and polyether blocks, B, wherein thepolyol block copolymer has the polyblock structure:

B-A′-Z′—Z—(Z′-A′-B)_(n)

wherein n=t−1 and wherein t=the number of terminal OH group residues onthe block A; and wherein each A′ is independently a polycarbonate chainhaving at least 70% carbonate linkages, and wherein each B isindependently a polyether chain and wherein Z′—Z—(Z′)_(n) is a starterresidue.

In the process according to the first aspect, the starter may be amonofunctional starter. In that case, for the avoidance of doubt, thepolyblock structure is:

B-A′-Z′—Z

The polycarbonate block comprises -A′- which may have the followingstructure:

wherein the ratio of p:q is at least 7:3; and

R^(e1) and R^(e2) depend on the nature of the epoxide used to prepareblocks A.

The polyether block B may have the following structure:

wherein

R^(e3) and R^(e4) depend on the nature of the epoxide used to prepareblocks B.

Each R^(e1), R^(e2), R^(e3), or R^(e4) may be independently selectedfrom H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl,alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl orheteroalkenyl, preferably selected from H or optionally substitutedalkyl.

R^(e1) and R^(e2) or R^(e3) and R^(e4) may together form a saturated,partially unsaturated or unsaturated ring containing carbon and hydrogenatoms, and optionally one or more heteroatoms.

As set out above, the nature of R^(e1), R^(e2), R^(e3) and R^(e4) willdepend on the epoxide used in the reaction. For example, if the epoxideis cyclohexene oxide (CHO), then R^(e1) and R^(e2) (or R^(e3) andR^(e4)) will together form a six membered alkyl ring (e.g. a cyclohexylring). If the epoxide is ethylene oxide, then R^(e1) and R^(e2) (orR^(e3) and R^(e4)) will be H. If the epoxide is propylene oxide, thenR^(e1) (or R^(e3)) will be H and R^(e2) (or R^(e4)) will be methyl (orR^(e1) (or R^(e3)) will be methyl and R^(e2) (or R^(e4)) will be H,depending on how the epoxide is added into the polymer backbone). If theepoxide is butylene oxide, then R^(e1) (or R^(e3)) will be H and R^(e2)(or R^(e4)) will be ethyl (or vice versa). If the epoxide is styreneoxide, then R^(e1) (or R^(e3)) may be hydrogen, and R^(e2) (or R^(e4))may be phenyl (or vice versa). If the epoxide is a glycidyl ether, thenR^(e1) (or R^(e3)) will be the ether group (—CH₂—OR₂₀) and R^(e2) (orR^(e4)) will be H (or vice versa). If the epoxide is a glycidyl ester,then R^(e1) (or R^(e3)) will be the ester group (—CH₂—OC(O)R₁₂) andR^(e2) (or R^(e4)) will be H (or vice versa). If the epoxide is aglycidyl carbonate, then R^(e1) (or R^(e3)) will be the carbonate group(CH₂—OC(O)OR₁₈) and R^(e2) (or R^(e4)) will be H (or vice versa).

It will also be appreciated that if a mixture of epoxides are used, theneach occurrence of R^(e1) and/or R^(e2) (or R^(e3) and/or R^(e4)) maynot be the same, for example if a mixture of ethylene oxide andpropylene oxide are used, R^(e1) (or R^(e3)) may be independentlyhydrogen or methyl, and R^(e2) (or R^(e4)) may be independently hydrogenor methyl.

Thus, R^(e1) and R^(e2) (or R^(e3) and R^(e4)) may be independentlyselected from hydrogen, alkyl or aryl, or R^(e1) and R^(e2) (or R^(e3)and R^(e4)) may together form a cyclohexyl ring, preferably R^(e1) andR^(e2) (or Rea and R^(e4)) may be independently selected from hydrogen,methyl, ethyl or phenyl, or R^(e1) and R^(e2) (or R^(e3) and R^(e4)) maytogether form a cyclohexyl ring.

The identity of Z and Z′ will depend on the nature of the startercompound.

The starter compound may be of the formula (III) as defined above.

Preferably, the polyol block copolymer has a molecular weight (Mn) inthe range of from about 300 to 20,000 Da, more preferably in the rangeof from about 400 to 8000 Da, most preferably from about 500-6000 Da.

The polycarbonate block, A, of the polyol block copolymer preferably hasa molecular weight (Mn) in the range of from about 200 to 4000 Da, morepreferably in the range of from about 200 to 2000 Da, most preferablyfrom about 200 to 1000 Da, especially from about 400 to 800 Da.

The polyether blocks, B, of the polyol block copolymer preferably have amolecular weight (Mn) in the range of from about 100 to 20,000 Da, morepreferably of from about 200 to 10,000 Da, most preferably from about200 to 5000 Da.

Alternatively, the polyether blocks B and hence also the polyol blockcopolymer may have a high molecular weight. The polyether blocks B mayhave a molecular weight of at least about 25,000 Daltons, such as atleast about 40,000 Daltons, e.g. at least about 50,000 Daltons, or atleast about 100,000 Daltons. High molecular weight polyol blockcopolymers formed by the method of the present invention may havemolecular weights above about 100,000 Daltons.

The Mn and hence the PDI of the polymers produced by the processes ofthe invention may be measured using Gel Permeation Chromatography (GPC).For example, the GPC may be measured using an Agilent 1260 Infinity GPCmachine with two Agilent PLgel μ-m mixed-D columns in series. Thesamples may be measured at room temperature (293K) in THF with a flowrate of 1 mL/min against narrow polystyrene standards (e.g. polystyrenelow EasiVials supplied by Agilent Technologies with a range of Mn from405 to 49,450 g/mol). Optionally, the samples may be measured againstpoly(ethylene glycol) standards, such as polyethylene glycol easivialssupplied by Agilent Technologies.

The polycarbonate block, A, of the polyol block copolymer may have atleast 76% carbonate linkages, preferably at least 80% carbonatelinkages, more preferably at least 85% carbonate linkages. Block A mayhave less than 98% carbonate linkages, preferably less than 97%carbonate linkages, more preferably less than 95% carbonate linkages.Optionally, block A has between 75% and 99% carbonate linkages,preferably between 77% and 95% carbonate linkages, more preferablybetween 80% and 90% carbonate linkages.

The polycarbonate block, A, of the polyol block copolymer may alsocomprise ether linkages. Block A may have less than 24% ether linkages,preferably less than 20% ether linkages, more preferably less than 15%ether linkages. Block A may have at least 1% ether linkages, preferablyat least 3% ether linkages, more preferably at least 5% ether linkages.Optionally, block A may have between 1% and 25% ether linkages,preferably between 5% and 20% ether linkages, more preferably between10% and 15% ether linkages.

Optionally, block A may be a generally alternating polycarbonate polyolresidue. If the epoxide is asymmetric, then the polycarbonate may havebetween 0-100% head to tail linkages, preferably between 40-100% head totail linkages, more preferably between 50-100%. The polycarbonate mayhave a statistical distribution of head to head, tail to tail and headto tail linkages in the order 1:2:1, indicating a non-stereoselectivering opening of the epoxide, or it may preferentially make head to taillinkages in the order of more than 50%, optionally more than 60%, morethan 70%, more than 80%, or more than 90%.

Optionally, block B comprises only ether linkages. Typically, block B isat least 90% derived, typically, at least 95% derived, more typically,at least 99%, most typically, 100% derived from epoxides and whereinoptionally the epoxides are selected from cyclohexene oxide, styreneoxide, ethylene oxide, propylene oxide, butylene oxide, substitutedcyclohexene oxides (such as limonene oxide, C10H16O or2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C11H22O), alkylene oxides(such as ethylene oxide and substituted ethylene oxides), unsubstitutedor substituted oxiranes (such as oxirane, epichlorohydrin,2-(2-methoxyethoxy)methyl oxirane (MEMO),2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO),2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO),1,2-epoxybutane, glycidyl ethers, vinyl-cyclohexene oxide,3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide,cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indeneoxide, and functionalized 3,5-dioxaepoxides.

Typically, block B has less than 10% carbonate linkages, typically, lessthan 5% carbonate linkages, more typically, less than 1% carbonatelinkages, most typically, 0% carbonate linkages.

Typically, block B has less than 10% carbonate linkages, typically, lessthan 5% carbonate linkages, more typically, less than 1% carbonatelinkages, most typically, 0% carbonate linkages.

The A block may have a high carbonate content and the B block a lowcarbonate content, for example, the A block may have greater than 70%carbonate linkages and/or, for example, the B block may have less than10% carbonate linkages, typically, less than 5% carbonate linkages, moretypically, less than 1% carbonate linkages, most typically, 0% carbonatelinkages.

Optionally, block A of the present invention may be a generallyalternating polycarbonate polyol residue.

Typically, the mol/mol ratio of block A to block B is in the range 25:1to 1:250. Typically the weight ratio of block A to block B is in therange 50:1 to 1:100.

Typically, block A, the polycarbonate block, is derived from epoxide andCO₂, more typically, epoxide and CO₂ provide at least 90% of theresidues in the block, especially, at least 95% of the residues in theblock, more especially, at least 99% of the residues in the block, mostespecially, about 100% of the residues in the block are residues ofepoxide and CO₂. Most typically, block A includes ethylene oxide and/orpropylene oxide residues and optionally other epoxide residues such ascyclohexylene oxide, butylene oxide, glycidyl ethers, glycidyl estersand glycidyl carbonates. At least 30% of the epoxide residues of block Amay be ethylene oxide or propylene oxide residues, typically, at least50% of the epoxide residues of block A are ethylene oxide or propyleneoxide residues, more typically, at least 75% of the epoxide residues ofblock A are ethylene oxide or propylene oxide residues, most typically,at least 90% of the epoxide residues of block A are ethylene oxide orpropylene oxide residues.

Typically, the carbonate of block A is derived from CO₂ i.e. thecarbonates incorporate CO₂ residues. Typically, block A has between70-100% carbonate linkages, more typically, 80-100%, most typically,90-100%.

Typically, block B, the polyethercarbonate block, is derived fromepoxides and CO₂. Typically, epoxide and CO₂ provide at least 90% of theresidues in the block, especially, at least 95% of the residues in theblock, more especially, at least 99% of the residues in the block, mostespecially, about 100% of the residues in the block are residues ofepoxide and CO₂. Most typically, block B includes ethylene oxide and/orpropylene oxide residues and optionally other epoxide residues such ascyclohexylene oxide, butylene oxide, glycidyl ethers, glycidyl estersand glycidyl carbonates. At least 30% of the epoxide residues of block Bmay be ethylene oxide or propylene oxide residues, typically, at least50% of the epoxide residues of block B are ethylene oxide or propyleneoxide residues, more typically, at least 75% of the epoxide residues ofblock B are ethylene oxide or propylene oxide residues, most typically,at least 90% of the epoxide residues of block B are ethylene oxide orpropylene oxide residues. According to the fourth aspect of theinvention, there is also provided a polyurethane produced from thereaction of a polyol block copolymer product of the process of the firstaspect of the present invention and a (poly)isocyanate. A polyurethanecan also be produced from the reaction of a composition comprising theproduct of the first aspect of the invention and a (poly)isocyanate. Thepolyurethane may be in the form of a soft foam, a flexible foam, anintegral skin foam, a high resilience foam, a viscoelastic or memoryfoam, a semi-rigid foam, a rigid foam (such as a polyurethane (PUR)foam, a polyisocyanurate (PIR) foam and/or a spray foam), an elastomer(such as a cast elastomer, a thermoplastic elastomer (TPU) or amicrocellular elastomer), an adhesive (such as a hot melt adhesive,pressure sensitive or a reactive adhesive), a sealant or a coating (suchas a waterborne or solvent dispersion (PUD), a two-component coating, aone component coating, a solvent free coating). The polyurethane may beformed via a process that involves extruding, moulding, injectionmoulding, spraying, foaming, casting and/or curing. The polyurethane maybe formed via a ‘one pot’ or ‘pre-polymer’ process.

Typically, the (poly)isocyanate comprises two or more isocyanate groupsper molecule. Preferably, the (poly)isocyanates are diisocyanates.However, the (poly)isocyanates may be higher (poly)isocyanates such astri isocyanates, tetraisocyanates, isocyanate polymers or oligomers, andthe like. The (poly)isocyanates may be aliphatic (poly)isocyanates orderivatives or oligomers of aliphatic (poly)isocyanates or may bearomatic (poly)isocyanates or derivatives or oligomers of aromatic(poly)isocyanates. Typically, the (poly)isocyanate component has afunctionality of 2 or more. In some embodiments, the (poly)isocyanatecomponent comprises a mixture of diisocyanates and higher isocyanatesformulated to achieve a particular functionality number for a givenapplication.

In some embodiments, the (poly)isocyanate employed has a functionalitygreater than 2. In some embodiments, such (poly)isocyanates have afunctionality between 2 to 5, more typically, 2-4, most typically, 2-3.

Suitable (poly)isocyanates which may be used include aromatic, aliphaticand cycloaliphatic polyisocyanates and combinations thereof. Suchpolyisocyanates may be selected from the group consisting of:1,3-Bis(isocyanatomethyl)benzene, 1,3-Bis(isocyanatomethyl)cyclohexane(H6-XDI), 1,4-cyclohexyl diisocyanate, 1,2-cyclohexyl diisocyanate,1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate,1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,1,6-hexamethylaminediisocyanate (HDI), isophorone diisocyanate (IPDI),2,4-toluene diisocyanate (TDI), 2,4,4-trimethylhexamethylenediisocyanate (TMDI), 2,6-toluene diisocyanate (TDI), 4,4′methylene-bis(cyclohexyl isocyanate) (H12MDI),naphthalene-1,5-diisocyanate, diphenylmethane-2,4′-diisocyanate (MDI),diphenylmethane-4,4′-diisocyanate (MDI),triphenylmethane-4,4′,4″triisocyanate, isocyanatomethyl-1,8-octanediisocyanate (TIN), m-tetramethylxylylene diisocyanate (TMXDI),p-tetramethylxylylene diisocyanate (TMXDI),Tris(p-isocyanatomethyl)thiosulfate, trimethylhexane diisocyanate lysinediisocyanate, m-xylylene diisocyanate (XDI), p-xylylene diisocyanate(XDI), 1,3,5-hexamethyl mesitylene triisocyanate,1-methoxyphenyl-2,4-diisocyanate, toluene-2,4,6-triisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate,4,4′-dimethyldiphenyl methane-2,2′,5,5′-tetraisocyanate and mixtures ofany two or more of these. In addition, the (poly)isocyanates may beselected from polymeric version of any of these isocyanates, these mayhave high or low functionality. Preferred polymeric isocyanates may beselected from MDI, TDI, and polymeric MDI.

The polyurethane of the fourth aspect may also comprise one or morechain extenders, which are typically low molecular weight polyols,polyamines or compounds with both amine and hydroxyl functionality knownin the art. Such chain extenders include ethylene glycol, 1,2-propyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,neopentyl glycol, trimethoxypropane (TMP), diethylene glycol,dipropylene glycol, diamines such as ethylenediamine,1,2-propylenediamine, 1,3-propylenediamine,N-methylpropylene-1,3-diamine, 2,4-tolylenediamine, 2,6 tolylenediamineand diethanolamine.

The composition comprising the product of the first aspect of theinvention may also comprise one or more additives from those known inthe art. The additives may include, but are not limited to, catalysts,blowing agents, stabilizers, plasticisers, fillers, flame retardants,defoamers, and antioxidants.

Fillers may be selected from mineral fillers or polymer fillers, forexample, styrene-acrylonitrile (SAN) dispersion fillers.

The blowing agents may be selected from chemical blowing agents orphysical blowing agents. Chemical blowing agents typically react with(poly)isocyanates and liberate volatile compounds such as CO₂. Physicalblowing agents typically vaporize during the formation of the foam dueto their low boiling points. Suitable blowing agents will be known tothose skilled in the art, and the amounts of blowing agent added can bea matter of routine experimentation. One or more physical blowing agentsmay be used or one or more chemical blowing agents may be used, inaddition one or more physical blowing agents may be used in conjunctionwith one or more chemical blowing agents.

Chemical blowing agents include water and formic acid. Both react with aportion of the (poly)isocyanate producing carbon dioxide which canfunction as the blowing agent. Alternatively, carbon dioxide may be useddirectly as a blowing agent, this has the advantage of avoiding sidereactions and lowering urea crosslink formation, if desired water may beused in conjunction with other blowing agents or on its own.

Typically, physical blowing agents for use in the current invention maybe selected from acetone, carbon dioxide, optionally substitutedhydrocarbons, and chloro/fluorocarbons. Chloro/fluorocarbons includehydrochlorofluorocarbons, chlorofluorocarbons, fluorocarbons andchlorocarbons. Fluorocarbon blowing agents are typically selected fromthe group consisting of: difluoromethane, trifluoromethane,fluoroethane, 1,1-difluoroethane, 1,1,1-trifluoroethane,tetrafluoroethanes difluorochloroethane, dichloromono-fluoromethane,1,1-dichloro-1-fluoroethane, 1,1-difluoro-1,2,2-trichloroethane,chloropentafluoroethane, tetrafluoropropanes, pentafluoropropanes,hexafluoropropanes, heptafluoropropanes, pentafluorobutanes.

Olefin blowing agents may be incorporated, namelytrans-1-chloro-3.3.3-trifluoropropene (LBA),trans-1,3,3,3-tetrafluoro-prop-1-ene (HFO-1234ze),2,3,3,3-tetrafluoro-propene (HFO-1234yf),cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz).

Typically, non-halogenated hydrocarbons for use as physical blowingagents may be selected from butane, isobutane, 2,3-dimethylbutane, n-and i-pentane isomers, hexane isomers, heptane isomers and cycloalkanesincluding cyclopentane, cyclohexane and cycloheptane. More typically,non-halogenated hydrocarbons for use as physical blowing agents may beselected from cyclopentane, iso-pentane and n-pentane.

Typically, where one or more blowing agents are present, they are usedin an amount of from about 0 to about 10 parts, more typically 2-6 partsof the total formulation. Where water is used in conjunction withanother blowing agent the ratio of the two blowing agents can varywidely, e.g. from 1 to 99 parts by weight of water in total blowingagent, preferably, 25 to 99+ parts by weight water Preferably, theblowing agent is selected from cyclopentane, iso-pentane, n-pentane.More preferably the blowing agent is n-pentane.

Typical plasticisers may be selected from succinate esters, adipateesters, phthalate esters, diisooctylphthalate (DIOP), benzoate estersand N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonic acid (BES).

Typical flame retardants will be known to those skilled in the art, andmay be selected from phosphonamidates,9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide (DOPO), chlorinatedphosphate esters, Tris(2-chloroisopropyl)phosphate (TCPP), Triethylphosphate (TEP), tris(chloroethyl) phosphate, tris(2,3-dibromopropyl)phosphate, 2,2-bis(chloromethyl)-1,3-propylene bis(di(2-chloroethyl)phosphate), tris(1,3-dichloropropyl) phosphate, tetrakis(2-chloroethyl)ethylene diphosphate, tricresyl phosphate, cresyl diphenyl phosphate,diammonium phosphate, melamine, melamine pyrophosphate, urea phosphate,alumina, boric acid, various halogenated compounds, antimony oxide,chlorendic acid derivatives, phosphorus containing polyols, brominecontaining polyols, nitrogen containing polyols, and chlorinatedparaffins. Flame retardants may be present in amounts from 0-60 parts ofthe total mixture.

According to the fifth aspect of the present invention, there is alsoprovided a polyurethane comprising a block copolymer residue having apolycarbonate block, A (-A′-Z′—Z—(Z′-A′)_(n)-), wherein A′ is apolycarbonate chain having at least 70% carbonate linkages and polyetherblocks, B, wherein the residue has a polyblock structureB-A′-Z′—Z—(Z′-A′-B)_(n), wherein n=t−1 and wherein t=the number ofterminal OH group residues on the block A and wherein Z′—Z-(E)_(n) is astarter residue.

The block copolymer residue of the polyurethane of the fifth aspect mayinclude any one or more features as defined above in relation to theproduct of the third aspect of the invention. According to the sixthaspect of the invention, there is also provided an isocyanate terminatedpolyurethane prepolymer comprising the reaction product of the polyolblock copolymer product of the process according to the first aspect ofthe present invention and an excess of (poly)isocyanate such as atleast >1 mole of isocyanate groups per mole OH groups.

According to the seventh aspect of the invention, there is provided anisocyanate terminated polyurethane prepolymer comprising a blockcopolymer residue having a polycarbonate block, A(-A′-Z′—Z—(Z′-A′)_(n)-), wherein A′ is a polycarbonate chain having atleast 70% carbonate linkages and polyether blocks, B, wherein theresidue has a polyblock structure B-A′-Z′—Z—(Z′-A′-B)_(n), wherein n=t−1and wherein t=the number of terminal OH group residues on the block A,and wherein Z′—Z—(Z′)_(n) is a starter residue.

The isocyanate terminated polyurethane prepolymer of the seventh aspectmay include any one or more features as defined above in relation to theproduct of the third aspect of the invention.

Catalysts that may be added to the polyol block copolymer product of theprocess of the first aspect of the present invention may be catalystsfor the reaction of (poly)isocyanates and a polyol. These catalystsinclude suitable urethane catalysts such as tertiary amine compoundsand/or organometallic compounds.

Optionally, a trimerisation catalyst may be used. An excess of(poly)isocyanate, or more preferably an excess of polymeric isocyanaterelative to polyol may be present so that polyisocyanurate ringformation is possible when in the presence of a trimerisation catalyst.Any of these catalysts may be used in conjunction with one or more othertrimerisation catalysts.

According to the eight aspect of the invention, there is provided acomposition comprising the polyol block copolymer according to the thirdaspect and one or more additives selected from catalysts, blowingagents, stabilizers, plasticisers, fillers, flame retardants, andantioxidants The composition may further comprise a (poly)isocyanate.

Typically, the catalysts for the (poly)isocyanate and the polyol blockcopolymer reaction include suitable urethane catalysts such as tertiaryamine compounds and/or organometallic compounds. Typically, atrimerisation catalyst is present.

An excess of (poly)isocyanate, more typically, an excess of polymericisocyanate relative to polyol may be present so that polyisocyanuratering formation in the presence of the trimerisation catalyst ispossible.

According to the ninth aspect of the invention, there is provided alubricant composition comprising a polyol block copolymer according tothe third aspect of the invention.

According to the tenth aspect of the invention, there is provided asurfactant composition comprising a polyol block copolymer according tothe third aspect of the invention.

Definitions

For the purpose of the present invention, an aliphatic group is ahydrocarbon moiety that may be straight chain (i.e. unbranched)branched, or cyclic and may be completely saturated, or contain one ormore units of unsaturation, but which is not aromatic. The term“unsaturated” means a moiety that has one or more double and/or triplebonds. The term “aliphatic” is therefore intended to encompass alkyl,cycloalkyl, alkenyl cycloalkenyl, alkynyl or cycloalkenyl groups, andcombinations thereof.

An aliphatic group is optionally a C₁₋₃₀ aliphatic group, that is, analiphatic group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbonatoms. Optionally, an aliphatic group is a C₁₋₈aliphatic, optionally aC₁₋₁₂aliphatic, optionally a C₁₋₁₀aliphatic, optionally a C₁₋₈aliphatic,such as a C₁₋₆aliphatic group. Suitable aliphatic groups include linearor branched, alkyl, alkenyl and alkynyl groups, and mixtures thereofsuch as (cycloalkyl)alkyl groups, (cycloalkenyl)alkyl groups and(cycloalkyl)alkenyl groups.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived by removal of a singlehydrogen atom from an aliphatic moiety. An alkyl group is optionally a“C₁₋₂₀ alkyl group”, that is an alkyl group that is a straight orbranched chain with 1 to 20 carbons. The alkyl group therefore has 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbonatoms. Optionally, an alkyl group is a C₁₋₁₅ alkyl, optionally a C₁₋₁₂alkyl, optionally a C₁₋₁₀ alkyl, optionally a C₁₋₈ alkyl, optionally aC₁₋₆ alkyl group. Specifically, examples of “C₁₋₂₀ alkyl group” includemethyl group, ethyl group, n-propyl group, iso-propyl group, n-butylgroup, iso-butyl group, sec-butyl group, tert-butyl group, sec-pentyl,iso-pentyl, n-pentyl group, neopentyl, n-hexyl group, sec-hexyl,n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecylgroup, n-dodecyl group, n-tridecyl group, n-tetradecyl group,n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecylgroup, n-nonadecyl group, n-eicosyl group, 1,1-dimethylpropyl group,1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group,n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropylgroup, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group,1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutylgroup, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutylgroup, 2-methylpentyl group, 3-methylpentyl group and the like.

The term “alkenyl,” as used herein, denotes a group derived from theremoval of a single hydrogen atom from a straight- or branched-chainaliphatic moiety having at least one carbon-carbon double bond. The term“alkynyl,” as used herein, refers to a group derived from the removal ofa single hydrogen atom from a straight- or branched-chain aliphaticmoiety having at least one carbon-carbon triple bond. Alkenyl andalkynyl groups are optionally “C₂₋₂₀alkenyl” and “C₂₋₂₀ alkynyl”,optionally “C₂₋₁₅ alkenyl” and “C₂₋₁₅ alkynyl”, optionally “C₂₋₁₂alkenyl” and “C₂₋₁₂ alkynyl”, optionally “C₂₋₁₀ alkenyl” and “C₂₋₁₀alkynyl”, optionally “C₂₋₈ alkenyl” and “C₂₋₈ alkynyl”, optionally “C₂₋₆alkenyl” and “C₂₋₆ alkynyl” groups, respectively. Examples of alkenylgroups include ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl,1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl and alkenyl. Examples ofalkynyl groups include ethynyl, 2-propynyl (propargyl) and 1-propynyl.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic” as usedherein refer to a saturated or partially unsaturated cyclic aliphaticmonocyclic or polycyclic (including fused, bridging and spiro-fused)ring system which has from 3 to 20 carbon atoms, that is an alicyclicgroup with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19or 20 carbon atoms. Optionally, an alicyclic group has from 3 to 15,optionally from 3 to 12, optionally from 3 to 10, optionally from 3 to 8carbon atoms, optionally from 3 to 6 carbons atoms. The terms“cycloaliphatic”, “carbocycle” or “carbocyclic” also include aliphaticrings that are fused to one or more aromatic or nonaromatic rings, suchas tetrahydronaphthyl rings, where the point of attachment is on thealiphatic ring. A carbocyclic group may be polycyclic, e.g. bicyclic ortricyclic. It will be appreciated that the alicyclic group may comprisean alicyclic ring bearing one or more linking or non-linking alkylsubstituents, such as —CH₂-cyclohexyl. Specifically, examples ofcarbocycles include cyclopropane, cyclobutane, cyclopentane,cyclohexane, bicycle[2,2,1]heptane, norborene, phenyl, cyclohexene,naphthalene, spiro[4.5]decane, cycloheptane, adamantane and cyclooctane.

A heteroaliphatic group (including heteroalkyl, heteroalkenyl andheteroalkynyl) is an aliphatic group as described above, whichadditionally contains one or more heteroatoms. Heteroaliphatic groupstherefore optionally contain from 2 to 21 atoms, optionally from 2 to 16atoms, optionally from 2 to 13 atoms, optionally from 2 to 11 atoms,optionally from 2 to 9 atoms, optionally from 2 to 7 atoms, wherein atleast one atom is a carbon atom. Optional heteroatoms are selected fromO, S, N, P and Si. When heteroaliphatic groups have two or moreheteroatoms, the heteroatoms may be the same or different.Heteroaliphatic groups may be substituted or unsubstituted, branched orunbranched, cyclic or acyclic, and include saturated, unsaturated orpartially unsaturated groups.

An alicyclic group is a saturated or partially unsaturated cyclicaliphatic monocyclic or polycyclic (including fused, bridging andspiro-fused) ring system which has from 3 to 20 carbon atoms, that is analicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19 or 20 carbon atoms. Optionally, an alicyclic group has from 3to 15, optionally from 3 to 12, optionally from 3 to 10, optionally from3 to 8 carbon atoms, optionally from 3 to 6 carbons atoms. The term“alicyclic” encompasses cycloalkyl, cycloalkenyl and cycloalkynylgroups. It will be appreciated that the alicyclic group may comprise analicyclic ring bearing one or more linking or non-linking alkylsubstituents, such as —CH₂-cyclohexyl. Specifically, examples of theC₃₋₂₀ cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.

A heteroalicyclic group is an alicyclic group as defined above whichhas, in addition to carbon atoms, one or more ring heteroatoms, whichare optionally selected from O, S, N, P and Si. Heteroalicyclic groupsoptionally contain from one to four heteroatoms, which may be the sameor different. Heteroalicyclic groups optionally contain from 5 to 20atoms, optionally from 5 to 14 atoms, optionally from 5 to 12 atoms.

An aryl group or aryl ring is a monocyclic or polycyclic ring systemhaving from 5 to 20 carbon atoms, wherein at least one ring in thesystem is aromatic and wherein each ring in the system contains three totwelve ring members. The term “aryl” can be used alone or as part of alarger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”. An arylgroup is optionally a “C₆₋₁₂ aryl group” and is an aryl groupconstituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includescondensed ring groups such as monocyclic ring group, or bicyclic ringgroup and the like. Specifically, examples of “C₆₋₁₀ aryl group” includephenyl group, biphenyl group, indenyl group, anthracyl group, naphthylgroup or azulenyl group and the like. It should be noted that condensedrings such as indan, benzofuran, phthalimide, phenanthridine andtetrahydro naphthalene are also included in the aryl group.

The term “heteroaryl” used alone or as part of another term (such as“heteroaralkyl”, or “heteroaralkoxy”) refers to groups having 5 to 14ring atoms, optionally 5, 6, or 9 ring atoms; having 6, 10, or 14 πelectrons shared in a cyclic array; and having, in addition to carbonatoms, from one to five heteroatoms. The term “heteroatom” refers tonitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogenor sulfur, and any quaternized form of nitrogen. The term “heteroaryl”also includes groups in which a heteroaryl ring is fused to one or morearyl, cycloaliphatic, or heterocyclyl rings, where the radical or pointof attachment is on the heteroaromatic ring. Examples include indolyl,isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl,benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl,phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl,acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-13]-1,4-oxazin-3(4H)-one. Thus, a heteroaryl group may bemono- or polycyclic. The term “heteroaralkyl” refers to an alkyl groupsubstituted by a heteroaryl, wherein the alkyl and heteroaryl portionsindependently are optionally substituted.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7-14-membered bicyclicheterocyclic moiety that is saturated, partially unsaturated, oraromatic and having, in addition to carbon atoms, one or more,optionally one to four, heteroatoms, as defined above. When used inreference to a ring atom of a heterocycle, the term “nitrogen” includesa substituted nitrogen.

Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groupsinclude but are not limited to cyclohexyl, phenyl, acridine,benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole,carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine,dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine,indole, indoline, indolizine, indazole, isoindole, isoquinoline,isoxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole,oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine,phenothiazine, phenoxazine, phthalazine, piperazine, piperidine,pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline,quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran,tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole,thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran,triazine, triazole, and trithiane.

The term “halide”, “halo” and “halogen” are used interchangeably and, asused herein mean a fluorine atom, a chlorine atom, a bromine atom, aniodine atom and the like, optionally a fluorine atom, a bromine atom ora chlorine atom, and optionally a fluorine atom.

A haloalkyl group is optionally a “C₁₋₂₀ haloalkyl group”, optionally a“C₁₋₁₆ haloalkyl group”, optionally a “C₁₋₁₂ haloalkyl group”,optionally a “C₁₋₁₀ haloalkyl group”, optionally a “C₁₋₆ haloalkylgroup”, optionally a “C₁₋₆ haloalkyl group” and is a C₁₋₂₀ alkyl, aC₁₋₁₅ alkyl, a C₁₋₁₂ alkyl, a C₁₋₁₀ alkyl, a C₁₋₈ alkyl, or a C₁₋₆ alkylgroup, respectively, as described above substituted with at least onehalogen atom, optionally 1, 2 or 3 halogen atom(s). The term “haloalkyl”encompasses fluorinated or chlorinated groups, including perfluorinatedcompounds. Specifically, examples of “C₁₋₂₀ haloalkyl group” includefluoromethyl group, difluoromethyl group, trifluoromethyl group,fluoroethyl group, difluoroethyl group, trifluoroethyl group,chloromethyl group, bromomethyl group, iodomethyl group and the like.

The term “acyl” as used herein refers to a group having a formula —C(O)Rwhere R is hydrogen or an optionally substituted aliphatic, aryl, orheterocyclic group.

An alkoxy group is optionally a “C₁₋₂₀ alkoxy group”, optionally a“C₁₋₁₅ alkoxy group”, optionally a “C₁₋₁₂ alkoxy group”, optionally a“C₁₋₁₀ alkoxy group”, optionally a “C₁₋₆ alkoxy group”, optionally a“C₁₋₆ alkoxy group” and is an oxy group that is bonded to the previouslydefined C₁₋₂₀ alkyl, C₁₋₁₅ alkyl, C₁₋₁₂ alkyl, C₁₋₁₀ alkyl, C₁₋₆ alkyl,or C₁₋₆ alkyl group respectively. Specifically, examples of “C₁₋₂₀alkoxy group” include methoxy group, ethoxy group, n-propoxy group,iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group,tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxygroup, n-hexyloxy group, iso-hexyloxy group, n-hexyloxy group,n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group,n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group,n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group,n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group,n-eicosyloxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxygroup, 2,2-dimethylpropoxy group, 2-methylbutoxy group,1-ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy group,1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxygroup, 2,3-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2-ethylbutoxygroup, 2-methylpentyloxy group, 3-methylpentyloxy group and the like.

An aryloxy group is optionally a “C₅₋₂₀ aryloxy group”, optionally a“C₆₋₁₂ aryloxy group”, optionally a “C₆₋₁₀ aryloxy group” and is an oxygroup that is bonded to the previously defined C₅₋₂₀ aryl, C₆₋₁₂ aryl,or C₆₋₁₀ aryl group respectively.

An alkylthio group is optionally a “C₁₋₂₀ alkylthio group”, optionally a“C₁₋₁₅ alkylthio group”, optionally a “C₁₋₁₂ alkylthio group”,optionally a “C₁₋₁₀ alkylthio group”, optionally a “C₁₋₈ alkylthiogroup”, optionally a “C₁₋₆ alkylthio group” and is a thio (—S—) groupthat is bonded to the previously defined C₁₋₂₀ alkyl, C₁₋₁₅ alkyl, C₁₋₁₂alkyl, C₁₋₁₀ alkyl, C₁₋₈ alkyl, or C₁₋₆ alkyl group respectively.

An arylthio group is optionally a “C₅₋₂₀ arylthio group”, optionally a“C₆₋₁₂ arylthio group”, optionally a “C₆₋₁₀ arylthio group” and is athio (—S—) group that is bonded to the previously defined C₅₋₂₀ aryl,C₆₋₁₂ aryl, or C₆₋₁₀ aryl group respectively.

An alkylaryl group is optionally a “C₆₋₁₂ aryl C₁₋₂₀ alkyl group”,optionally a “C₆₋₁₂ aryl C₁₋₁₆ alkyl group”, optionally a “C₆₋₁₂ arylC₁₋₆ alkyl group” and is an aryl group as defined above bonded at anyposition to an alkyl group as defined above. The point of attachment ofthe alkylaryl group to a molecule may be via the alkyl portion and thus,optionally, the alkylaryl group is —CH₂-Ph or —CH₂CH₂-Ph. An alkylarylgroup can also be referred to as “aralkyl”.

A silyl group is optionally Si(R_(s))₃, wherein each R_(s) can beindependently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. Optionally, each R_(s) isindependently an unsubstituted aliphatic, alicyclic or aryl. Optionally,each R_(s) is an alkyl group selected from methyl, ethyl or propyl.

A silyl ether group is optionally a group OSi(R₆)₃ wherein each R₆ canbe independently an aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl or heteroaryl group as defined above. Each R₆ canbe independently an unsubstituted aliphatic, alicyclic or aryl.Optionally, each R₆ is an optionally substituted phenyl or optionallysubstituted alkyl group selected from methyl, ethyl, propyl or butyl(such as n-butyl (nBu) or tert-butyl (tBu)). Exemplary silyl ethergroups include OSi(Me)₃, OSi(Et)₃, OSi(Ph)₃, OSi(Me)₂(tBu), OSi(tBu)₃and OSi(Ph)₂(tBu). A nitrile group (also referred to as a cyano group)is a group CN.

An imine group is a group CRNR, optionally CHNR, wherein R₇ is analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. R₇ may be unsubstituted aliphatic,alicyclic or aryl. Optionally R₇ is an alkyl group selected from methyl,ethyl or propyl.

An acetylide group contains a triple bond —C≡C—R₉, optionally wherein R₉can be hydrogen, an aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl or heteroaryl group as defined above. For thepurposes of the invention when R₉ is alkyl, the triple bond can bepresent at any position along the alkyl chain. R₉ may be unsubstitutedaliphatic, alicyclic or aryl. Optionally R₉ is methyl, ethyl, propyl orphenyl.

An amino group is optionally —NH₂, —NHIR₁₀ or —N(R₁₀)₂ wherein R₁₀ canbe an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silylgroup, aryl or heteroaryl group as defined above. It will be appreciatedthat when the amino group is N(R₁₀)₂, each R₁₀ group can be the same ordifferent. Each R₁₀ may independently an unsubstituted aliphatic,alicyclic, silyl or aryl. Optionally R₁₀ is methyl, ethyl, propyl, SiMe₃or phenyl.

An amido group is optionally —NR₁₁C(O)— or C(O)—NR₁₁— wherein R₁₁ can behydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. R₁₁ may be unsubstitutedaliphatic, alicyclic or aryl. Optionally R₁₁ is hydrogen, methyl, ethyl,propyl or phenyl. The amido group may be terminated by hydrogen, analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group.

Unless defined otherwise herein, an ester group is optionally —OC(O)R₁₂—or —C(O)OR₁₂— wherein R₁₂ can be an aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.R₁₂ may be unsubstituted aliphatic, alicyclic or aryl. Optionally R₁₂ ismethyl, ethyl, propyl or phenyl. The ester group may be terminated by analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group. It will be appreciated that if R₁₂ is hydrogen, thenthe group defined by —OC(O)R₁₂— or —C(O)OR₁₂— will be a carboxylic acidgroup.

A sulfoxide is optionally S(O)R₁₃ and a sulfonyl group is optionallyS(O)₂R₁₃ wherein R₁₃ can be an aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl or heteroaryl group as defined above. R₁₃ may beunsubstituted aliphatic, alicyclic or aryl. Optionally R₁₃ is methyl,ethyl, propyl or phenyl.

A carboxylate group is optionally —OC(O)R₁₄, wherein R₁₄ can behydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. R₁₄ may be unsubstitutedaliphatic, alicyclic or aryl. Optionally R₁₄ is hydrogen, methyl, ethyl,propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl,pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.

An acetamide is optionally MeC(O)N(R₁₅)₂ wherein R₁₅ can be hydrogen, analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. R₁₅ may be unsubstituted aliphatic,alicyclic or aryl. Optionally R₁₅ is hydrogen, methyl, ethyl, propyl orphenyl.

A phosphinate group is optionally —OP(O)(R₁₆)₂ or —P(O)(OR₁₆)(R₁₆)wherein each R₁₆ is independently selected from hydrogen, or analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. R₁₆ may be aliphatic, alicyclic oraryl, which are optionally substituted by aliphatic, alicyclic, aryl orC₁₋₆alkoxy. Optionally R₁₆ is optionally substituted aryl or C₁₋₂₀alkyl, optionally phenyl optionally substituted by C₁₋₆alkoxy(optionally methoxy) or unsubstituted C₁₋₂₀alkyl (such as hexyl, octyl,decyl, dodecyl, tetradecyl, hexadecyl, stearyl). A phosphonate group isoptionally P(O)(OR₁₆)₂ wherein R₁₆ is as defined above. It will beappreciated that when either or both of R₁₆ is hydrogen for the groupP(O)(OR₁₆)₂, then the group defined by P(O)(OR₁₆)₂ will be a phosphonicacid group.

A sulfinate group is optionally S(O)OR₁₇ or OS(O)R₁₇ wherein R₁₇ can behydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic,heteroalicyclic, aryl or heteroaryl group as defined above. R₁₇ may beunsubstituted aliphatic, alicyclic or aryl. Optionally R₁₇ is hydrogen,methyl, ethyl, propyl or phenyl. It will be appreciated that if R₁₇ ishydrogen, then the group defined by S(O)OR₁₇ will be a sulfonic acidgroup.

A carbonate group is optionally —OC(O)OR₁₈, wherein R₁₈ can be hydrogen,an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. Ria may be optionally substitutedaliphatic, alicyclic or aryl. Optionally R₁₈ is hydrogen, methyl, ethyl,propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl,pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl oradamantyl. It will be appreciated that if R₁₇ is hydrogen, then thegroup defined by —OC(O)OR₁₈ will be a carbonic acid group.

A carbonate functional group is —OC(O)O— and may be derived from asuitable source. Generally, it is derived from CO₂.

In an -alkylC(O)OR₁₉ or alkylC(O)R₁₉ group, R₁₉ can be hydrogen, analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. R₁₉ may be unsubstituted aliphatic,alicyclic or aryl. Optionally R₁₉ is hydrogen, methyl, ethyl, propyl,butyl (for example n-butyl, isobutyl or tert-butyl), phenyl,pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.

An ether group is optionally —OR₂₀ wherein R₂₀ can be an aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group asdefined above. R₂₀ may be unsubstituted aliphatic, alicyclic or aryl.Optionally R₂₀ is methyl, ethyl, propyl, butyl (for example n-butyl,isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,trifluoromethyl or adamantyl.

It will be appreciated that where any of the above groups are present ina Lewis base G, one or more additional R groups may be present, asappropriate, to complete the valency. For example, in the context of anamino group, an additional R group may be present to give RNHR₁₀,wherein R is hydrogen, an optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group asdefined above. Optionally, R is hydrogen or aliphatic, alicyclic oraryl.

As used herein, the term “optionally substituted” means that one or moreof the hydrogen atoms in the optionally substituted moiety is replacedby a suitable substituent. Unless otherwise indicated, an “optionallysubstituted” group may have a suitable substituent at each substitutableposition of the group, and when more than one position in any givenstructure may be substituted with more than one substituent selectedfrom a specified group, the substituent may be either the same ordifferent at every position. Combinations of substituents envisioned bythis invention are optionally those that result in the formation ofstable compounds. The term “stable”, as used herein, refers to compoundsthat are chemically feasible and can exist for long enough at roomtemperature i.e. (16-25° C.) to allow for their detection, isolationand/or use in chemical synthesis.

Optional substituents for use in the present invention include, but arenot limited to, halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy,aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido,imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl,acetylide, phosphinate, sulfonate or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups(for example, optionally substituted by halogen, hydroxy, nitro,carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile,silyl, sulfoxide, sulfonyl, phosphinate, sulfonate or acetylide).

It will be appreciated that although in formula (V), the groups X and Gare illustrated as being associated with a single M₁ or M₂ metal centre,one or more X and G groups may form a bridge between the M₁ and M₂ metalcentres.

For the purposes of the present invention, the epoxide substrate is notlimited. The term epoxide therefore relates to any compound comprisingan epoxide moiety (i.e. a substituted or unsubstituted oxiranecompound). Substituted oxiranes include monosubstituted oxiranes,disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstitutedoxiranes. Epoxides may comprise a single oxirane moiety. Epoxides maycomprise two or more oxirane moieties.

It will be understood that the term “an epoxide” is intended toencompass one or more epoxides. In other words, the term “an epoxide”refers to a single epoxide, or a mixture of two or more differentepoxides. For example, the epoxide substrate may be a mixture ofethylene oxide and propylene oxide, a mixture of cyclohexene oxide andpropylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or amixture of ethylene oxide, propylene oxide and cyclohexene oxide.

The term polyethercarbonate block polyether polyol generally refers topolymers which are substantially terminated at each end with —OH, —SH,and/or —NHR′ groups (encompassing C—OH, P—OH, —C(O)OH, etc. moieties).R′ may be H, or optionally substituted alkyl, heteroalkyl, aryl,heteroaryl, cycloalkyl or heterocycloalkyl, optionally R′ is H oroptionally substituted alkyl.

By way of example, at least about 90%, at least about 95%, at leastabout 98% or at least about 99% of polymers may be terminated at eachend with —OH groups. The skilled person will appreciate that if thepolymer is linear, then it may be capped at both ends with —OH groups.If the polymer is branched, each of the branches may be capped with —OHgroups. Such polymers are generally useful in preparing higher polymerssuch as polyurethanes. The chains may comprise a mixture of functionalgroups (e.g. —OH and —SH) groups, or may contain the same functionalgroup (e.g. all —OH groups).

The term “continuous” used herein can be defined as the mode of additionof materials or may refer to the nature of the reaction method as awhole.

In terms of continuous mode of addition, the relevant materials arecontinually or constantly added during the course of a reaction. Thismay be achieved by, for example, adding a stream of material with eithera constant flow rate or with a variable flow rate. In other words, theone or more materials are added in an essentially non-stop fashion. Itis noted, however, that non-stop addition of the materials may need tobe briefly interrupted for practical considerations, for example torefill or replace a container of the materials from which thesematerials are being added.

By a semi-batch mode of addition is meant that at least one of thereagents is not added in a single portion but is added in a plurality ofportions or continuously/discontinuously.

By neutral or alkaline pH is meant that the product has a pH of greaterthan or equal to 7 when dissolved in water.

In terms of a whole reaction being continuous, the reaction may beconducted over a long period of time, such as a number of days, weeks,months, etc. In such a continuous reaction, reaction materials may becontinually topped-up and/or products of the reaction may be tapped-off.It will be appreciated that although catalysts may not be consumedduring a reaction, catalysts may in any case require topping-up, sincetapping-off may deplete the amount of catalyst present.

A continuous reaction may employ continuous addition of materials.

A continuous reaction may employ a discontinuous (i.e. batch-wise orsemi batch-wise) addition of materials

The term series used herein refers to when two or more reactors areconnected so that the crude reaction mixture can flow from the firstreactor to the second reactor.

The term nested used herein refers to when two or more reactors areconfigured so that one is located within the other. For example in thepresent invention, when the second reactor is located inside the firstreactor, allowing the conditions of both reactors to influence theother.

Methods

Gel Permeation Chromatography

GPC measurements were carried out against narrow polydispersitypoly(ethylene glycol) or polystyrene standards in THF using an Agilent1260 Infinity machine equipped with Agilent PLgel Mixed-D columns.

EXAMPLES Example 1

Hexanediol (2.6 g) was taken into a 100 mL reactor and dried at 120° C.under vacuum for 1 hour. A mixture of catalyst (1) (0.15 g) in PO (12.45g) injected into the vessel. The vessel was heated to 75° C. andpressurised to 10 bar and stirred for 16 hours after which it was cooledand vented, resulting in a ca. 550 g/mol PPC-polyol. The contents of thereactor were then transferred to a clean, dry Schlenk along with PO (3mL) and EtOAc (9 mL) and kept under N₂.

In a separate 100 mL reactor, 9.2 mg of DMC catalyst as perWO2017/037441 example 1 and PPG400 (0.88 g) were dried at 120° C. undervacuum for 1 hour. The reactor was cooled down to room temperature andethyl acetate (12 mL) was injected into the vessel via a syringe undercontinuous flow of N₂ gas. The vessel was heated to the desiredtemperature (130° C.). 3.75 g of propylene oxide was added in 3 bursts(1.25 g each) with 30 minutes between each to confirm activity of theDMC catalyst.

The reactor was cooled to 70° C. whilst pressurising to 1 bar with N₂and PO (1.25 g) was added. The Schlenk mixture from above was then addedvia a HPLC pump. added over 1 hour. The reaction was carried out over 5hours. The reactor was cooled to below 10° C. and the pressure wasreleased. NMR and GPC were measured immediately.

TABLE 1 Experimental results from Example 1 Overall Mn Example CO₂ wt %g/mol PDI 1 10.8 1850 1.10

Examples 2-10

Examples 2-10 were carried out as per example 1 except they wereperformed in a 2 L reactor. Reaction 1 was carried out using thequantities detailed in Table 2.

Reaction 2 was carried out in a 2 L reactor using the quantities shownin Table 3. The reactor minimum fill requirements met by addition ofeither Ethyl acetate (280 mL) or polycarbonate ether polyol from apreceding dual reactor reaction. The mixture was stirred and heated to130° C. DMC catalyst was activated using 15 g of propylene oxide wasadded in 3 bursts (5 g each) with −10 minutes between each to confirmactivity of the DMC catalyst. The PPC/PO mixture from above was thenadded at 85° C. via a HPLC pump added over 1-3 hours.

Following PPC addition, a further quantity of PO was then added to themixture via HPLC at 5 mL/min. The reaction was “cooked out” for afurther 1-16 hours before being cooled to below 10° C. and any pressurereleased. NMR and GPC were measured immediately.

TABLE 2 Reagent quantities and conditions for reaction 1 Reaction 1 Cat-Set Set alyst Starter/ EtOAc/ Temp/ Pressure/ E.g PO/g (1)/g Starter g gC. barg  2 544 6.0 DPG 114 150 75 20  3 544 4.3 DPG 42.43 0 75 20  4 5442.5 DPG 47 0 75 20  5 544 2.9 Hex 40 180 74 20  6 664 2.7 DPG 47.5 0 717.7  7 415 4.0 TMPEO450 55 0 65 10  8 300 2.9 TMPEO450 54.59 0 65 10  9300 2.9 TMPEO450 85.22 0 65 10 10 498 1.4 TMPEO450 42.33 0 65 10

TABLE 3 Reagent quantities and conditions for reaction 2 Reaction 2Final Minimum Post PPC Cookout CO2 PCE E.g. Starter Starter/g DMC/g fillPO/g time (h) wt % length PDI  2 DPG 2.5 0.15 EtOAc 30 2 17.3%  700 1.13 3 DPG 2.5 0.07 EtOAc 30 1   24% 2000 1.14  4 DPG 2.5 0.07 EtOAc 90 1  17% 2000 1.12  5 Hex 2.2 0.15 EtOAc 23 2   21% 1900 1.12  6 N/A N/A0.10 PCE polyol  0 1 16.1% 2000 1.15  7 PPG400 2.2 0.10 EtOAc 30 1   26%3700 1.56  8 PPG400 2.2 0.10 EtOAc 30 1   16% 3400 1.50  9 PPG400 2.20.10 EtOAc 30 1   9% 2700 1.19 10 PPG400 2.2 0.10 EtOAc 30 1 10.8% 41001.33

The examples demonstrate that the low molecular weight polycarbonatepolyols, which have poor stability, do not have to be stored or purifiedbut can be produced and used in situ to produce more stable polyols withhigh overall CO₂ contents containing a mixture carbonate and etherlinkages, under low CO₂ pressures in reactor 1 (see examples 6 to 10).Furthermore, the process can produce polymers with CO₂ contents in thecore of the polymer and higher ether contents at the end of the polyols.

Examples 7-10 demonstrate the process can be used to produce polyolswith higher functionality as trimethylolpropane ethoxylate (Mn 450,triol) was used as the starter in reaction 1.

Example 6 demonstrates the process tolerates using the final polyolproduct as the ‘starter’ to activate the DMC catalyst in reactor 2. Thismethod demonstrates that the reaction ‘heel’ of a previous reaction canbe left in the reactor to activate the DMC for the next reaction andsatisfy the minimum fill of the reactor. This is particularly useful inmanufacturing to eliminate the need for solvent or a different starterto pre-activate the DMC with.

The thermal stability of a PPC polyol as produced in reaction 1 (Mn2000) was compared against a polyol of the invention produced by example5 (FIG. 1). It can be clearly seen that the block copolymer polyolproduced by the dual reaction has enhanced thermal stability compared tothe PPC polyol.

1. A process for producing a polyol block copolymer in a multiplereactor system; the system comprising a first and second reactor whereina first reaction takes place in the first reactor and a second reactiontakes place in the second reactor; wherein the first reaction is thereaction of a carbonate catalyst with CO₂ and epoxide, in the presenceof a starter and/or solvent to produce a polycarbonate polyol copolymerand the second reaction is the reaction of a DMC catalyst with thepolycarbonate polyol compound of the first reaction and epoxide toproduce a polyol block copolymer, wherein (i) the product of the firstreaction is fed into the second reactor as a crude reaction mixture,(ii) the epoxide and the polycarbonate polyol compound of the firstreaction are fed into the second reactor in a continuous or semi-batchmanner, and/or (iii) the product of the first reaction has a neutral oralkaline pH on addition to the second reaction.
 2. A process forproducing a polyol block copolymer in a multiple reactor system; thesystem comprising a first and second reactor wherein a first reactiontakes place in the first reactor and a second reaction takes place inthe second reactor; wherein the first reaction is the reaction of acarbonate catalyst with CO₂ and epoxide, in the presence of apolyfunctional starter, and optionally a solvent, to produce apolycarbonate polyol and the second reaction is the semi-batch orcontinuous reaction of a DMC catalyst with the polycarbonate polyolcompound of the first reaction and epoxide to produce a polyol blockcopolymer.
 3. A process for producing a polyol block copolymer accordingto claim 2, wherein the starter compound has the formula (III):Z—(R^(Z))_(a)(III) wherein Z can be any group which can have 2 or more—R^(Z) groups attached to it and may be selected from optionallysubstituted alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene,hererocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Zmay be a combination of any of these groups, for example Z may be analkylarylene, heteroalkylarylene, heteroalkylheteroarylene oralkylheteroarylene group; a is an integer which is at least 2; whereineach R^(Z) may be —OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), —PR′(O)(OH)₂or —PR′(O)OH, optionally R^(Z) is selected from —OH, —NHR′ or —C(O)OH,optionally each R^(z) is —OH, —C(O)OH or a combination thereof (e.g.each R^(z) is —OH); wherein R′ may be H, or optionally substitutedalkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl,optionally R′ is H or optionally substituted alkyl.
 4. The processaccording to claim 1, wherein the DMC catalyst is pre-activated,optionally in the second reactor or separately, optionally wherein theDMC is pre-activated with a starter compound or with the reactionproduct of the first or second reaction or with a polycarbonate polyolcopolymer or with a polyol block copolymer.
 5. (canceled)
 6. (canceled)7. The process according to claim 1, wherein the product of the firstreaction is a low molecular weight polycarbonate polyol product having amolecular weight (Mn) in the range 200 to 4000 Daltons as measured byGel Permeation Chromatography (GPC).
 8. (canceled)
 9. (canceled)
 10. Theprocess according to claim 1, wherein the product of the first reactionis fed into the second reactor, as a crude reaction mixture, whereinsaid second reactor contains a pre-activated DMC catalyst.
 11. Theprocess according to claim 1, wherein the polycarbonate copolymer is fedinto the reaction with the DMC catalyst, as a crude reaction mixture,wherein said reaction contains a pre-activated DMC catalyst.
 12. Theprocess according to claim 1, wherein the first reaction is carried outunder CO₂ pressure of less than 20 bar.
 13. (canceled)
 14. The processaccording to claim 1, wherein the first reaction is a batch, semi-batch,or continuous process.
 15. The process according to claim 1, wherein thesecond reaction is a continuous process or semi batch process.
 16. Theprocess according to claim 1, wherein the crude reaction mixture fedinto the second reactor includes an amount of unreacted epoxide and/orstarter.
 17. The process according to claim 1, wherein the carbonatecatalyst is present in the crude reaction mixture.
 18. The processaccording to claim 1, wherein the carbonate catalyst has been removedfrom the crude reaction mixture prior to the addition to the secondreactor.
 19. The process according to claim 1, wherein the temperatureof reaction in the first reactor is in the range about 0° C. to 250° C.20. The process according to claim 1, wherein the temperature ofreaction in the second reactor is in the range from about 50 to about160° C.
 21. The process according to claim 1, wherein the reactors arelocated in series.
 22. The process according to claim 1, wherein thereactors are nested.
 23. The process according to claim 1, wherein thefirst and second reactors are effective to provide different reactionconditions, such as temperature and/or pressure, to each othersimultaneously.
 24. (canceled)
 25. The process according to claim 1,wherein the epoxides are selected from cyclohexene oxide, styrene oxide,ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexeneoxides (such as limonene oxide, C₁₀H₁₆O or2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C₁₁H₂₂O), alkylene oxides(such as ethylene oxide and substituted ethylene oxides), unsubstitutedor substituted oxiranes (such as oxirane, epichlorohydrin,2-(2-methoxyethoxy)methyl oxirane (MEMO),2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO),2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO),1,2-epoxybutane, glycidyl ethers, glycidyl esters, glycidyl carbonates,vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 2,3-epoxybutane,isobutylene oxide, cyclopentene oxide,2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, andfunctionalized 3,5-dioxaepoxides.
 26. (canceled)
 27. The processaccording to claim 1, wherein the carbonate catalyst is a catalystcapable of producing polycarbonate chains with greater than 76%carbonate linkages.
 28. The process according to claim 1, wherein thecarbonate catalyst is a metal catalyst comprising phenol or phenolateligands. 29-36. (canceled)
 37. The process according to claim 1, whereinthe DMC catalyst is based upon Zn₃[Co(CN)₆]₂ (zinc hexacyanocobaltate).38-40. (canceled)
 41. The process according to claim 1, wherein theproduct of the first reaction is used to pre-activate the DMC catalystin the second reaction, prior to addition of epoxide.
 42. The processaccording to claim 1, wherein the same or different epoxides are used inthe first or second reactions.
 43. The process according to claim 1,wherein the epoxide used in the first or second reaction comprisespropylene oxide, ethylene oxide or a mixture of propylene oxide andethylene oxide.
 44. (canceled)
 45. The process according to claim 1,wherein the second reaction is carried substantially in the absence ofCO₂.
 46. The process according to claim 1, wherein the polyol blockcopolymer produced in the second reaction is a polycarbonate blockpolyether polyol block copolymer.
 47. A polyol block copolymercomprising a polycarbonate block, A (-A′-Z′—Z—(Z′-A′)_(n)-), andpolyether blocks, B, wherein the polyol block copolymer has thepolyblock structure:B-A′-Z′—Z—(Z′-A′-B)_(n) wherein n=t−1 and wherein t=the number ofterminal OH group residues on the block A; and t=at least 2; and whereineach A′ is independently a polycarbonate chain having at least 70%carbonate linkages, and wherein each B is independently a polyetherchain; and wherein Z′—Z—(Z′)_(n) is a starter residue.
 48. The polyolblock copolymer according to claim 47, wherein -A′- has the followingstructure:

wherein the ratio of p:q is at least 7:3; and block B has the followingstructure:

and R^(e1), R^(e2), R^(e3) and R^(e4) depend on the nature of theepoxide used to prepare blocks A and B. 49-69. (canceled)
 70. Apolyurethane produced from the reaction of a polyol block copolymerproduced according to the process of claim 1 and a (poly)isocyanate. 71.A polyurethane comprising a block copolymer residue having apolycarbonate block, A (-A′-Z′—Z—(Z′-A′)_(n)-), wherein A′ is apolycarbonate chain having at least 70% carbonate linkages, andpolyether blocks, B, wherein the residue has a polyblock structureB-A′-Z′—Z—(Z′-A′-B)_(n), wherein n=t−1 and wherein t=the number ofterminal OH group residues on the block A and wherein Z′—Z—(Z′)n is astarter residue. 72-83. (canceled)
 84. A lubricant compositioncomprising a polyol block copolymer of claim
 47. 85. A surfactantcomposition comprising a polyol block copolymer of claim 47.